EP1782780A1 - Procédé de fabrication d'un mélange exothermique, mélange exothermique, composition exothermique et article exothermique - Google Patents

Procédé de fabrication d'un mélange exothermique, mélange exothermique, composition exothermique et article exothermique Download PDF

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Publication number
EP1782780A1
EP1782780A1 EP05765809A EP05765809A EP1782780A1 EP 1782780 A1 EP1782780 A1 EP 1782780A1 EP 05765809 A EP05765809 A EP 05765809A EP 05765809 A EP05765809 A EP 05765809A EP 1782780 A1 EP1782780 A1 EP 1782780A1
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EP
European Patent Office
Prior art keywords
heat generating
water
generating composition
shape
mixture
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Application number
EP05765809A
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German (de)
English (en)
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EP1782780A4 (fr
Inventor
Toshihiro MYCOAL PRODUCTS CORPORATION DODO
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Mycoal Products Corp
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Mycoal Products Corp
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Publication of EP1782780A1 publication Critical patent/EP1782780A1/fr
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F7/00—Heating or cooling appliances for medical or therapeutic treatment of the human body
    • A61F7/02—Compresses or poultices for effecting heating or cooling
    • A61F7/03—Compresses or poultices for effecting heating or cooling thermophore, i.e. self-heating, e.g. using a chemical reaction
    • A61F7/032—Compresses or poultices for effecting heating or cooling thermophore, i.e. self-heating, e.g. using a chemical reaction using oxygen from the air, e.g. pocket-stoves
    • A61F7/034—Flameless
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/16—Materials undergoing chemical reactions when used
    • C09K5/18—Non-reversible chemical reactions
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24V—COLLECTION, PRODUCTION OR USE OF HEAT NOT OTHERWISE PROVIDED FOR
    • F24V30/00—Apparatus or devices using heat produced by exothermal chemical reactions other than combustion
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F7/00—Heating or cooling appliances for medical or therapeutic treatment of the human body
    • A61F2007/0098—Heating or cooling appliances for medical or therapeutic treatment of the human body ways of manufacturing heating or cooling devices for therapy
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F7/00—Heating or cooling appliances for medical or therapeutic treatment of the human body
    • A61F7/02—Compresses or poultices for effecting heating or cooling
    • A61F2007/0268—Compresses or poultices for effecting heating or cooling having a plurality of compartments being filled with a heat carrier

Definitions

  • the present invention relates to a process for producing a heat generating mixture having exothermic characteristics such that it is excellent in exothermic rising properties and having excellent moldability and resistance to compression by bringing at least essential components of a heat generating composition into contact with an oxidizing gas, which is capable of being industrially put into practical use, a heat generating mixture, a heat generating composition and a heat generating body.
  • throwaway body warmers are well known as a product to be used by the action of a mixture of an iron powder and a reaction aid, etc. with air (oxygen).
  • an iron powder is the most general. Salt, water, or the like is used as the reaction aid, and it is also well known that active carbon, vermiculite, diatomaceous earth, wood meal, or a water absorptive polymer is mixed as a water retaining agent for carrying such a substance thereon and used.
  • Patent Document 1 proposes a heat generating composition in which manganese dioxide, cupric oxide and triiron tetroxide are mixed with other heat generating composition components. These substances function as a catalyst and cannot be used as an exothermic substance. Furthermore, in the case where these substances are added in a heat generating composition, the contact between triiron tetroxide, etc. and the surface of an iron powder is not sufficient so that the described effects are not so revealed.
  • Patent Document 2 proposes a heat generating body in which after reaching 40 °C, a heat generating composition containing, as major components, iron, water and an oxidation promoter such as salt is accommodated in an air-permeable container. However, it takes 25 minutes for making this heat generating composition reach 40 °C, and therefore, industrial mass production thereof was difficult.
  • Patent Document 3 proposes a throwaway body warmer comprising a heat generating composition having shape holding properties by adding a powdered thickener such as corn starch and potato starch.
  • Patent Document 4 proposes a solid heat generating composition prepared by mixing a binding agent such as CMC in a powdered heat generating composition and compression molding the mixture.
  • Patent Document 5 proposes an ink-like and/or creamy heat generating composition to which viscosity is given by using a thickener and a heat generating body and a process for producing the same.
  • compositions were excellent with respect to prevention of deviation and moldability, their exothermic performance was remarkably deteriorated. That is, even when liberated water is absorbed in a support, a covering material, a water absorptive material, etc., the heat generating composition is viscous due to the binding agent, the thickener, the flocculant aid, the excipient, or the like. Thus, the reaction became slow, or a rapid temperature rise to a prescribed temperature or warming over a long period of time was difficult because the liberated water hardly comes out, or the thickener or the like adversely affects the exothermic substances.
  • conventionally used powdered or particulate heat generating compositions do not have moldability because surplus water is not present or insufficient.
  • these powdered or particulate heat generating compositions are good in exothermic characteristics, since a heat generating body is formed by filling such a composition in an air-permeable accommodating bag, the exothermic temperature distribution is not constant due to deviation of the heat generating composition or the like, the feeling for use is worse, and it is difficult to produce a heat generating body having a shape adaptive to the shape of a body to be heat insulated. Thus, their exothermic performance could not be sufficiently exhibited.
  • Patent Document 1 JP-A-53-60885
  • Patent Document 2 JP-A-57-10673
  • Patent Document 3 JP-A-6-343658
  • Patent Document 4 JP-A-59-189183
  • Patent Document 5 JP-A-9-75388
  • a problem of the invention is to provide a process for producing an active heat generating mixture capable of causing an oxidation reaction immediately upon contact with air to generate heat and subsequently initiating an abrupt reaction which after arrival at a certain fixed temperature, is then changed to a mild reaction, the heating generating mixture being cheap and being able to be industrially mass-produced; a heat generating mixture; a heat generating composition; a moldable heat generating composition; and a heat generating body.
  • a process for producing a heat generating mixture of the invention is characterized by bringing a reaction mixture containing, as essential components, an iron powder, a reaction accelerator and water and having a water content of from 0.5 to 20 % by weight and a water mobility value showing an amount of surplus water of less than 0.01 with an oxidizing gas under circumstances at 0 °C or higher and regulating a temperature rise of the reaction mixture at 1 °C or higher within 10 minutes.
  • a process for producing a heat generating mixture as set forth in claim 2 is characterized in that in the process for producing a heat generating mixture as set forth in claim 1, an amount of the reaction accelerator is from 2 to 6 parts by weight based on 100 parts by weight of the total sum of the reaction accelerator and water.
  • a process for producing a heat generating mixture as set forth in claim 3 is characterized in that in the process for producing a heat generating mixture as set forth in claim 1, the reaction mixture is embedded in an air-permeable sheet-like material such as non-woven fabrics and subjected to a contact treatment with the oxidizing gas.
  • a heat generating mixture of the invention is characterized by being produced by the production process as set forth in claim 1.
  • a heat generating composition of the invention is characterized in that the heat generating mixture as set forth in claim 4 is used as a raw material; the water content is adjusted; an iron powder, a carbon component, a reaction accelerator and water are contained as essential components; and a water mobility value thereof is from 0.01 to 20.
  • a heat generating composition as set forth in claim 6 is characterized in that in the heat generating composition as set forth in claim 5, the heat generating composition contains at least one member selected from additional components consisting of a water retaining agent, a water absorptive polymer, a pH adjusting agent, a hydrogen formation inhibitor, an aggregate, a fibrous material, a functional substance, a surfactant, an organosilicon compound, a pyroelectric substance, a moisturizer, a fertilizer component, a hydrophobic polymer compound, a heat generating aid, a metal other than iron, a metal oxide other than iron oxide, an acidic substance, and a mixture thereof.
  • additional components consisting of a water retaining agent, a water absorptive polymer, a pH adjusting agent, a hydrogen formation inhibitor, an aggregate, a fibrous material, a functional substance, a surfactant, an organosilicon compound, a pyroelectric substance, a moisturizer, a fertilizer component, a hydropho
  • a heat generating body of the invention is characterized in that the heat generating composition as set forth in claim 5 is accommodated in an air-permeable accommodating bag to form an exothermic part.
  • a heat generating body as set forth in claim 8 is characterized in that in the heat generating body as set forth in claim 7, the accommodated heat generating composition is a heat generating composition molded body.
  • a heat generating body as set forth in claim 9 is characterized in that in the heat generating body as set forth in claim 7, the air-permeable accommodating bag is constituted of a substrate and an air-permeable covering material, the heat generating composition is sectioned into plural parts, and the periphery of the heat generating composition is sealed to form plural sectional exothermic parts.
  • a heat generating body as set forth in claim 10 is characterized in that in the heat generating body as set forth in claim 8, the shape of at least member selected from the heat generating composition molded body, the sectional exothermic part and the exothermic part is a shape selected from the group consisting of a circular shape, an elliptical shape, a polygonal shape, a star shape, and a flower shape with respect to the planar shape and is a shape selected from the group consisting of a polygonal pyramidal shape, a conical shape, a frustum shape, a spherical shape, a parallelepiped shape, a cylindrical shape, a semi-pillar shape, a semicylindroid shape, a semicylidrical shape, a pillar shape, and a cylindroid shape with respect to the three-dimensional shape.
  • a heat generating body as set forth in claim 11 is characterized in that in the heat generating body as set forth in claim 7, fixing means is provided in at least
  • the heat generating composition does not contain a flocculant aid, a flocculant, an agglomeration aid, a dry binder, a dry binding agent, a dry binding material, a sticky raw material, a thickener, and an excipient. Also, in the heat generating body, it is preferable that the heat generating composition molded body is subjected to a compression treatment.
  • the fixing means is an adhesive layer and that the adhesive layer contains at least one member selected from additional components consisting of a water retaining agent, a water absorptive polymer, a pH adjusting agent, a surfactant, an organosilicon compound, a hydrophobic polymer compound, a pyroelectric substance, an antioxidant, an aggregate, a carbon component, a fibrous material, a moisturizer, a functional substance, and a mixture thereof.
  • additional components consisting of a water retaining agent, a water absorptive polymer, a pH adjusting agent, a surfactant, an organosilicon compound, a hydrophobic polymer compound, a pyroelectric substance, an antioxidant, an aggregate, a carbon component, a fibrous material, a moisturizer, a functional substance, and a mixture thereof.
  • Embodiments of a process for producing a heat generating mixture by a contact treatment of a reaction mixture with an oxidizing gas, a heat generating mixture, a heat generating composition, and a heat generating body will be described below in detail.
  • the invention is to establish a production process capable of achieving mass production by using a reaction mixture containing, as essential components, an iron powder, a reaction accelerator and water and having a water content of from 0.5 to 20 % by weight and a water mobility value showing an amount of surplus water of less than 0.01, thereby raising a reaction rate at the time of a contact treatment with an oxidizing gas and making it possible to achieve a temperature rise of the reaction mixture of 1 °C or higher within a time of 10 minutes.
  • a heat generating composition whose water mobility value has been regulated at from 0.01 to 50 by adding a carbon component or the like to a heat generating mixture produced by the contact treatment of the reaction mixture with an oxidizing agent or adjusting the water content is properly sticky, has excellent moldability and is applicable with a molding method such as a force-through molding method and a cast molding method, whereby heat generating bodies having various shapes can be produced.
  • a heat generating composition having a water mobility value of from 0.01 to 20 is so excellent that it initiates an exothermic reaction immediately upon contact with air, has excellent exothermic rising properties and has excellent moldability.
  • the contact treatment method of the reaction mixture with an oxidizing gas is not particularly limited so far as it is able to contact treat a reaction mixture containing, as essential components, an iron powder, a reaction accelerator and water and having a water content of from 0.5 to 20 % by weight and a water mobility value of less than 0.01 with an oxidizing gas and regulate a temperature rise of the reaction mixture at 1 °C or more.
  • Specific examples thereof include:
  • the water content in the reaction mixture or the heat generating mixture prior to the treatment with an oxidizing gas is usually from 0.5 to 20 % by weight, preferably from 1 to 15 % by weight, more preferably from 2 to 10 % by weight, further preferably from 3 to 10 % by weight, and still further preferably from 6 to 10 % by weight.
  • the temperature of the reaction mixture after the contact with an oxidizing gas is not limited so far as the temperature rise is regulated at 1 °C or more.
  • the temperature of the reaction mixture after the contact with an oxidizing gas is preferably from 1 to 80 °C, more preferably from 1 to 70 °C, further preferably from 1 to 60 °C, and still further preferably from 1 to 40 °C.
  • the circumferential temperature at the time of contact between the reaction mixture and the oxidizing gas is not limited so far as the temperature of the reaction mixture is raised to a prescribed temperature or higher.
  • the circumferential temperature at the time of contact between the reaction mixture and the oxidizing gas is preferably 0 °C or higher, more preferably from 0 to 250 °C, further preferably from 10 to 200 °C, still further preferably from 20 to 150 °C, even further preferably from 25 to 100 °C, and even still further preferably from 25 to 50 °C.
  • the time of contact between the reaction mixture and the oxidizing gas is not limited so far as the time required for regulating a temperature rise at 1 °C or more is within 10 minutes.
  • the time of contact between the reaction mixture and the oxidizing gas is preferably from one second to 10 minutes, more preferably from one second to 7 minutes, further preferably from one second to 5 minutes, still further preferably from 2 seconds to 5 minutes, even further preferably from 2 seconds to 3 minutes, and even still further preferably from 2 seconds to one minute.
  • the temperature of the oxidizing gas is not limited so far as the foregoing circumferential temperature is kept.
  • the "water mobility value” as referred to herein is a value showing an amount of surplus water which can transfer to the outside of the heat generating composition in water present in the heat generating composition.
  • This water mobility value will be described below with reference to Figs. 13 to 17.
  • a filter paper 18 of No. 2 second class of JIS P3801 in which eight lines are drawn radiating from the central point with an interval of 45° is placed on a stainless steel plate 22 as shown in Figs.
  • a template 19 having a size of 150 mm in length x 100 mm in width and having a hollow cylindrical hole 20 having a size of 20 mm in inner diameter x 8 mm in height is placed in the center of the filter paper 18; a sample 21 is placed in the vicinity of the hollow cylindrical hole 20; and a stuffer plate 14 is moved on and along the template 19 and inserted into the hollow cylindrical hole 20 while stuffing the sample 21, thereby leveling the sample (force-in die molding).
  • a non-water absorptive 70 ⁇ m-thick polyethylene film 17 is placed so as to cover the hole 20, and a flat plate 16 made of stainless steel having a size of 5 mm in thickness x 150 mm in length x 150 mm in width is further placed thereon and held for 5 minutes such that an exothermic reaction is not caused. Thereafter, a shown in Fig. 17, the filter paper 18 is taken out, and an oozed-out locus of the water or aqueous solution is read as a distance 23 (unit: mm) from a periphery 24 as an edge of the hollow cylindrical hole to an oozed-out tip along the radiating lines. Similarly, a distance 23 from each of the lines is read, and eight values in total are obtained.
  • Each of the eight values (a, b, c, d, e, f, g and h) which are read out is defined as a measured water content value.
  • An arithmetic average value of the eight measured water content values is defined as a water content value (mm) of the sample.
  • the water content for the purpose of measuring a real water content value is defined as a compounded water content of the heat generating composition corresponding to the weight of the heat generating composition having a size of 20 mm in inner diameter x 8 mm in height or the like, similar measurement is conducted only with water corresponding to that water content, and a value as calculated in the same manner is defined as a real water content value (mm).
  • a value obtained by dividing the water content value by the real water content value and then multiplying with 100 is a water mobility value. That is, the water mobility value is represented by the following expression.
  • Water mobility value ⁇ [ Water content value mm ] / [ Real water content value mm ] ⁇ 100
  • five points are measured, and the five water mobility values are averaged, thereby defining an average value thereof as a water mobility value of the sample.
  • a percentage of water content of the heat generating composition is calculated through measurement of the water content of the heat generating composition by an infrared moisture meter, a water content necessary for the measurement is calculated on the basis of the percentage of water content, and a real water content value is measured and calculated from the foregoing water content.
  • the water mobility value (0 to 100) is preferably from 0.01 to 20, more preferably from 0.01 to 18, further preferably from 0.01 to 15, still further preferably from 0.01 to 13, even further preferably from 1 to 13, and even still further preferably from 3 to 13.
  • a heat generating composition having a water mobility value of less than 0.01 is insufficient in moldability.
  • a heat generating composition having a water mobility value of from 0.01 to 50 has moldability and therefore, is a moldable heat generating composition.
  • the water mobility value exceeds 20 it is necessary that a part of water of the heat generating composition is removed by water absorption, dehydration, etc. That is, unless a part of water in the heat generating composition molded body is removed by water absorption, dehydration, etc.
  • the "water mobility value" as referred to herein is a value obtained by digitizing surplus water which is the water content capable of being easily and freely oozed out the system in water which is contained in the heat generating composition or mixture or the like.
  • the amount of the surplus water is variously changed depending the amount of a component having a water retaining ability such as a water retaining agent, a carbon component and a water absorptive polymer and wettability of each component, and therefore, it is every difficult to predict the water mobility value from the amount of addition of water.
  • the amount of surplus water of the heat generating composition or mixture of the like is determined from the water mobility value, by determining the amount of addition of water and the amount of other components, a heat generating composition or mixture or the like having a substantially fixed amount of surplus water is obtained with good reproducibility. That is, by previously examining the water mobility value and a composition ratio of a heat generating composition or mixture or the like, a heat generating composition or mixture or the like as compounded along that composition ratio has a water mobility value falling within a fixed range, namely, an amount of surplus water falling within a fixed range.
  • heat generating compositions such as a powdered heat generating composition which causes heat generation upon contact with air but does not have moldability, a heat generating composition which causes heat generation upon contact with air and has moldability, and a heat generating composition which, after discharging out a fixed amount of surplus water from the system by water absorption, etc. , causes heat generation upon contact with air and has moldability.
  • the water mobility value is known, it is possible to note what state does the subject heat generating composition or mixture or the like take. If the water mobility value is employed, it is possible to embody a desired state with good reproducibility by a simple measurement. Thus, it becomes possible to determine a component ratio of the heat generating composition on the basis of the water mobility value obtained by the measurement and the component ratio, thereby simply achieving actual production of a heat generating composition.
  • water (or a reaction accelerator aqueous solution) is added to and mixed with a mixture of specified amounts of heat generating composition components exclusive of water (or a reaction accelerator aqueous solution), thereby producing plural heat generating compositions having a different water content.
  • a water mobility value of each of the heat generating compositions is measured, thereby determining a relationship between the amount of addition of water (or a reaction accelerator aqueous solution) and a water mobility value.
  • a heat generating composition which has moldability and causes heat generation upon contact with air has a water mobility value of from 0.01 to 20.
  • a moldable heat generating composition in which water does not function as a barrier layer and which has moldability causes heat generation upon contact with air can be produced with good reproducibility.
  • surplus water is used as a connecting substance and a flocculant aid or a dry binding material is not used, reaction efficiency of the iron powder does not drop.
  • an exothermic performance can be obtained in a small amount as compared with the case of using a flocculant aid or a dry binding material.
  • what water does not function as a barrier layer and causes an exothermic reaction upon contact with air means that water in a heat generating composition does not function as a barrier layer which is an air intercepting layer and immediately after the production of a heat generating composition, comes into contact with air, thereby immediately causing an exothermic reaction.
  • a moldable heat generating composition containing this surplus water as a connecting substance, it becomes possible to produce, for example, a super thin and super flexible heat generating body having plural sectional exothermic parts of a heat generating composition molded body on a substantially planar substrate in a maximum width of preferably from 1 to 50 mm, and more preferably from 1 to 20 mm, or in a maximum diameter of preferably from 1 to 50 mm, and more preferably from 1 to 20 mm (in the case where two or more axes are present as in an ellipse, the major axis is dealt as a length, while the minor axis is dealt as a width).
  • the "surplus water” as referred to herein means water or an aqueous solution portion which is present excessively in the heat generating composition and easily transfers to the outside of the heat generating composition.
  • the surplus water is defined as a water mobility value which is a value of water or a value of an aqueous solution portion sucked out from the heat generating composition, etc. by a filter paper.
  • the "moldability" as referred to in the invention exhibits that a molded body of the heat generating composition having a cavity or concave die shape is formed by force-through molding using a trimming die having a cavity or cast molding using a concave die, whereby after molding including mold release, the molding shape of the heat generating composition molded body is held.
  • the moldability is revealed, since the shape is held until the heat generating composition molded article is at least covered by a covering material and a seal part is formed between the substrate and the covering material, sealing can be achieved in the periphery of the shape with a desired shape. Also, since so-called “spots" which are a collapsed piece of the heat generating composition are not scattered in the seal part, the sealing can be achieved without causing cutting in seal. The presence of the spots causes insufficient sealing.
  • the "moldable heat generating composition” as referred to herein means a heat generating composition which contains, as essential components, an iron powder, a reaction accelerator and water, does not contain a flocculant aid, a flocculant, an agglomeration aid, a dry binder, a dry binding agent, a dry binding material, a sticky binder, a thickener, and an excipient, has surplus water so as to have a water mobility value of from 0.01 to 20 and has moldability by the surplus water as a connecting substance; in which the water in the heat generating composition does not function as a barrier layer; and which causes an exothermic reaction upon contact with air.
  • the "resistance to compression” as referred to herein means that a heat generating composition compressed body obtained by compressing a heat generating composition molded body having a heat generating composition accommodated in a molding die within the die to such an extent that the heat generating composition compressed body having a thickness of 70 % of the die thickness holds 80 % or more of exothermic rising properties of the exothermic rising properties of the heat generating composition molded body prior to the compression (a difference in temperature between one minute and 3 minutes after starting a heat generation test of the heat generating composition).
  • the measurement method of exothermic rinsing properties for the resistance to compression will be described below.
  • the thickness after compression is preferably from 50 to 99.5 %, more preferably from 60 to 99.5 %, and further preferably from 60 to 95 % of the die thickness.
  • the particle size of the water-insoluble solid component separation is conducted using a sieve, and the particle size of the component which has passed through the sieve is calculated from an opening of the sieve. That is, sieves of 8, 12, 20, 32, 42, 60, 80, 100, 115, 150, 200, 250 and 280 meshes and a receiving dish are combined in this order from up to down. About 50 g of water-insoluble solid component particles are placed on the uppermost 8-mesh sieve and shaken for one minute using an automatic shaker. Weights of the water-insoluble solid component particles on each of the sieves and the receiving dish are weighed. The total amount thereof is defined as 100 %, and the particle size distribution is determined from weight fractions.
  • the size ( ⁇ m) calculated from the opening of the specific mesh is defined as the particle size of the water-insoluble solid component.
  • each of the mesh sieves may be combined with other mesh sieves.
  • the particles which have passed through a 16-mesh sieve are defined to have a particle size of not more than 1 mm; the particles which have passed through a 20-mesh sieve are defined to have a particle size of not more than 850 ⁇ m; the particles which have passed through a 48-mesh sieve are defined to have a particle size of not more than 300 ⁇ m; the particles which have passed through a 60-mesh sieve are defined to have a particle size of not more than 250 ⁇ m; the particles which have passed through a 65-mesh sieve are defined to have a particle size of not more than 200 ⁇ m; the particles which have passed through an 80-mesh sieve are defined to have a particle size of not more than 180 ⁇ m; the particles which have passed through a 100-mesh sieve are defined to have a particle size of not more than 150 ⁇ m; the particles which have passed through a 115-mesh sieve are defined to have a particle size of not more than 120 ⁇ m; the particles which have passed through
  • any gas can be used as the oxidizing gas so far as it is oxidizing.
  • examples thereof include an oxygen gas, air, and mixed gases of an inert gas (for example, a nitrogen gas, an argon gas, and a helium gas) and an oxygen gas.
  • the mixed gas is not limited so far as it contains oxygen, mixed gases containing 10 % or more of an oxygen gas are preferable, and of these, air is especially preferable.
  • a catalyst such as platinum, palladium, iridium, and mixtures thereof can also be used.
  • the oxidation reaction can be carried out under stirring in an oxidizing gas atmosphere optionally under a pressure and/or upon irradiation of ultrasonic waves. The optimal condition of the oxidation reaction may be properly experimentally determined.
  • An amount of the oxidizing gas to be used is not limited but may be adjusted depending upon the kind of the oxidizing gas, the kind and particle size of the iron powder, the water content, the treatment temperature, the treatment method, and the like.
  • an open system there is no limitation so far as a necessary amount of oxygen can be taken in.
  • the system may be surrounded by an air-permeable raw material such as non-woven fabrics and woven fabrics. So far as the system is in an air-permeable state, it is to be noted that the system is an open system.
  • the amount of air is preferably from 0.01 to 1, 000 L/min, more preferably from 0.01 to 100 L/min, and further preferably from 0.1 to 50 L/min per 200 g of the iron powder under one atmosphere.
  • the amount of the oxidizing gas may be reduced into the concentration of oxygen on the basis of the case of air.
  • a peroxide may be added. Examples of the peroxide include hydrogen peroxide and ozone.
  • the state of the reaction mixture or heat generating mixture at the time of the contact treatment with an oxidizing gas may be any of a standing state, a transfer state, or a fluidizing state by stirring, etc. and may be properly selected.
  • the circumstances at the time of mixing the respective components of the reaction mixture, the heat generating mixture or the heat generating composition and at the time of the contact treatment with a mixed oxidizing gas at the time of adjusting the water content are not limited, and examples thereof include those in an oxidizing gas atmosphere and those in blowing of an oxidizing gas.
  • a heat generating composition As a method for measuring a temperature rise of the heat generating composition, a heat generating composition is allowed to stand in a state that it is sealed in an air-impermeable outer bag for one hour under a condition that the circumferential temperature is 20 ⁇ 1 °C.
  • the heat generation test of the heat generating body follows the JIS temperature characteristic test.
  • the iron powder is not limited, and examples thereof include cast iron powders, atomized iron powders, electrolyzed iron powders, reduced iron powders, sponge iron powders, and iron alloy powders thereof.
  • the iron powder may contain carbon and oxygen, and an iron powder containing 50 % or more of iron and other metals may be employed.
  • the kind of the metal which is contained as an alloy, etc. is not particularly limited so far as the iron component works as a component of the heat generating composition. Examples of such a metal include metals such as aluminum, manganese, copper, nickel, silicon, cobalt, palladium, and molybdenum, and semiconductors.
  • the metal of the invention includes a semiconductor. Such a metal or alloy may be contained only in the surface or the interior, or may be contained in both the surface and the interior.
  • An iron powder containing a carbon component and/or covered by a carbon component is also preferable as the iron powder.
  • a proportion of the carbon component is not limited so far as a ratio of the iron component to the carbon component is 50 % by weight or more, an iron powder in which the surface thereof is partially covered by from 0.3 to 3.0 % by weight of a conductive carbonaceous substance is useful.
  • the conductive carbonaceous substance include carbon black, active carbon, carbon nanotubes, carbon nanohorns, and fullerens. Ones which have become conductive by doping are also employable.
  • the iron powder include reduced iron powders, atomized iron powders, and sponge iron powders. In particular, the case where the conductive carbonaceous substance is active carbon and the iron powder is a reduced iron powder is useful for a heat generating body.
  • the content of the metal other than iron is usually from 0.01 to 50 % by weight, and preferably from 0.1 to 10 % by weight based on the whole of the iron powder. Furthermore, in order to efficiently carry out covering by a conductive carbonaceous substance, an oil such as a spindle oil may be added in an amount of from 0.01 to 0.05 % by weight to such an extent that the fluidity of the iron powder is not hindered.
  • the iron powder in the heat generating composition may also be calculated from the iron powder in the reaction mixture or heat generating mixture.
  • the "iron oxide film” as referred to herein is a film made of oxygen-containing iron such as iron oxide, hydroxide or oxyhydroxide. Furthermore, in the invention, it is thought that the active iron powder forms an iron oxide film at least locally on the surface of the iron powder, from which an oxidation reaction promoting effect is obtained by a local cell as formed between an iron matrix and an iron oxide film or a pit inside and outside the iron oxide film.
  • the reaction accelerator is not particularly limited so far as it is able to promote the reaction of the heat generating substance.
  • Examples thereof include metal halides, nitrates, acetates, carbonates, and metal sulfates.
  • metal halides include sodium chloride, potassium chloride, magnetic chloride, calcium chloride, ferrous chloride, ferric chloride, sodium bromide, potassium bromide, ferrous bromide, ferric bromide, sodium iodide, and potassium iodide.
  • nitrates include sodium nitrate and potassium nitrate.
  • Examples of acetates include sodium acetate.
  • Examples of carbonates include ferrous carbonate.
  • metal sulfates include potassium sulfate, sodium sulfate, and ferrous sulfate.
  • the water one from a proper source may be employed. Its purity and kind and the like are not particularly limited.
  • the content of water is preferably from 1 to 60 % by weight, more preferably from 1 to 40 % by weight, further preferably from 7 to 40 % by weight, still further preferably from 10 to 35 % by weight, and even further preferably from 20 to 30 % by weight of the heat generating composition.
  • the content of water is preferably from 0.5 to 20 % by weight, more preferably from 1 to 20 % by weight, further preferably from 5 to 20 % by weight, and still further preferably from 7 to 15 % by weight of the reaction mixture or heat generating mixture.
  • the heat generating composition or mixture may be measured according to the following items.
  • the heat generating composition molded body includes a heat generating composition compressed body, except for the case where the heat generating composition molded body and the heat generating composition compressed body are distinguishingly used.
  • the amount of the reaction accelerator is from 1.0 to 5.0 parts by weight and the amount of water is from 0.5 to 20 parts by weight based on 100 parts by weight of the iron powder (in the case of an iron powder having an iron oxide film, an iron powder as reduced in terms of an iron component amount).
  • the amount of the carbon component is from 1.0 to 50 parts by weight; the amount of the water retaining agent is from 0.01 to 10 parts by weight; the amount of the water absorptive polymer is from 0.01 to 20 parts by weight; the amount of the pH adjusting agent is from 0.01 to 5 parts by weight; the amount of the hydrogen formation inhibitor is from 0.01 to 12 parts by weight; the amount of each of the aggregate, the fibrous material and the functional substance is from 0.01 to 10 parts by weight; the amount of the surfactant is from 0.01 to 5 parts by weight; the amount of each of the organosilicon compound, the pyroelectric substance, the moisturizer, the fertilizer component, the hydrophobic polymer compound, the anti-foaming agent, the heat generating aid, the metal other than iron and the metal oxide other than iron oxide is from 0.01 to 10 parts by weight; and the amount of the acidic substance is from 0.001 to 1 parts by weight, respectively.
  • the anti-foaming agent there are enumerated not only usual pH adjusting agents such as poly(sodium phosphate) but also those which are used in this field.
  • the reaction mixture of the invention contains, as essential components, an iron powder, a reaction accelerator and water and may further contain at least one member selected from additional components consisting of a carbon component, a water retaining agent, a water absorptive polymer, a pH adjusting agent, a hydrogen formation inhibitor, an aggregate, a fibrous material, a functional substance, a surfactant, an organosilicon compound, a pyroelectric substance, a moisturizer, a fertilizer component, a hydrophobic polymer compound, a heat generating aid, a metal other than iron, a metal oxide other than iron oxide, an acidic substance, and a mixture thereof.
  • additional components consisting of a carbon component, a water retaining agent, a water absorptive polymer, a pH adjusting agent, a hydrogen formation inhibitor, an aggregate, a fibrous material, a functional substance, a surfactant, an organosilicon compound, a pyroelectric substance, a moisturizer, a fertilizer component, a hydro
  • the carbon component is not particularly limited so far as it contains carbon as a component. Examples thereof include carbon black, graphite, active carbon, carbon nanotubes, carbon nanohorns, and flullerenes. Carbon which has become conductive by doping or the like is also employable. There are enumerated active carbons as prepared from coconut shell, wood, charcoal, coal, bone carbon, etc. and carbons as prepared from other raw materials such as animal products, natural gases, fats, oils, and resins. In particular, active carbons having an adsorption retaining ability are preferable. Furthermore, it is not always required that the carbon component is present alone. In the case where an iron powder containing the carbon component and/or covered by the carbon component is used in the heat generating composition, it is to be noted that the heat generating composition contains the carbon component even though the carbon component is not present alone.
  • the water retaining agent is not limited so far as it is able to retain water.
  • examples thereof include porous materials derived from plants having high capillary function and hydrophilicity such as wood meal, pulp powder, active carbon, saw dust, cotton cloth having a number of cotton fluffs, short fiber of cotton, paper dust, and vegetable materials, water-containing magnesium silicate based clay minerals such as active clay and zeolite, pearlite, vermiculite, silica based porous substances, coralline stone, and volcanic ash based substances (for example, terraballoon, shirasu balloon, and taisetsu balloon).
  • the water retaining agent may be subjected to a processing treatment such as baking and/or pulverization.
  • the water absorptive polymer is not particularly limited so far as it is a resin having a crosslinking structure and having a water absorption magnification of ion-exchanged water of 3 times or more of the dead weight. Furthermore, a water absorptive polymer the surface of which is crosslinked may be employed. Conventionally known water absorptive polymers and commercial products may also be employed.
  • water absorptive polymer examples include poly(meth)acrylic acid crosslinked materials, poly(meth)-acrylic acid salt crosslinked materials, sulfonic group-containing poly(meth)acrylic ester crosslinked materials, polyoxyalkylene group-containing poly(meth)acrylic ester crosslinked materials, poly(meth)acrylamide crosslinked materials, crosslinked materials of a copolymer of a (meth)acrylic acid salt and a (meth)acrylamide, crosslinked materials of a copolymer of a hydroxyalkyl (meth) acrylate and a (meth)acrylic acid salt, polydioxolane crosslinked materials, crosslinked polyethylene oxide, crosslinked polyvinylpyrrolidone, sulfonated polystyrene crosslinked materials, crosslinked polyvinylpyridine, saponification products of a starch-poly (meth) acrylonitrile graft copolymer, starch-poly(meth)acrylic acid (
  • water absorptive polymers having biodegradation properties are not limited so far as they are a biodegradable water absorptive polymer.
  • examples thereof include polyethylene oxide crosslinked materials, polyvinyl alcohol crosslinked materials, carboxymethyl cellulose crosslinked materials, alginic acid crosslinked materials, starch crosslinked materials, polyamino acid crosslinked materials, and polylactic acid crosslinked materials.
  • the pH adjusting agent is not limited so far it is able to adjust the pH.
  • examples thereof include alkali metal weak acid salts and hydroxides and alkaline earth metal weak acid salts and hydroxides such as Na 2 CO 3 , NaHCO 3 , Na 3 PO 4 , Na 2 HPO 4 , Na 5 P 3 O 10 , NaOH, KOH, Ca(OH) 2 , Mg(OH) 2 , and Ca 3 (PO 4 ) 2 .
  • the hydrogen formation inhibitor is not limited so far as it is able to inhibit the formation of hydrogen.
  • Examples thereof include one member or two or more members selected from the group consisting of sulfur compounds, oxidizing agents, alkaline substances, sulfur, antimony, selenium, phosphorus, and tellurium.
  • sulfur compounds include compounds with an alkali metal or an alkaline earth metal, metal sulfides such as calcium sulfide, metal sulfites such as sodium sulfite, and metal thiosulfates such as sodium thiosulfate.
  • the alkaline substance is not limited so far as it is a substance exhibiting alkalinity.
  • examples thereof include silicates, phosphates, sulfites, thiosulfates, carbonates, hydrogencarbonates, hydroxides, Na 3 PO 4 , and Ca(OH) 2 .
  • the aggregate is not limited so far as it is useful as a filler and/or is useful for making the heat generating composition porous.
  • Examples thereof include fossilized coral (for example, coral fossil and weathered coral fossil), bamboo charcoal, bincho charcoal, silica-alumina powders, silica-magnesia powders, kaolin, crystalline cellulose, colloidal silica, pumice, silica gel, silica powders, mica powders, clays, talc, synthetic resin powders or pellets, foamed synthetic resins such as foamed polyesters or polyurethanes, diatomaceous earth, alumina, and cellulose powder.
  • kaolin and crystalline cellulose are not contained in the heat generating composition of the invention but contained only in the case of using as an adhesive.
  • the fibrous material is an inorganic fibrous material and/or an organic fibrous material.
  • examples thereof include rock wool, glass fibers, carbon fibers, metal fibers, pulps, papers, non-woven fabrics, woven fabrics, natural fibers such as cotton and hemp, regenerated fibers such as rayon, semi-synthetic fibers such as acetates, synthetic fibers, and pulverized products thereof.
  • the functional substance is not limited so far as it is a substance having any function. Examples thereof include at least one member selected from minus ion emitting substances and far infrared ray radiating substances.
  • the minus ion emitting substance is not limited so far as it emits a minus ion as a result either directly or indirectly, and examples thereof include ferroelectric substances such as tourmaline, fossilized coral, granite, and calcium strontium propionate, and ores containing a radioactive substance such as radium and radon.
  • the far infrared ray radiating substance is not limited so far as it radiates far infrared rays.
  • Examples thereof include ceramics, alumina, zeolite, zirconium, and silica.
  • the surfactant includes anionic surfactants, cationic surfactants, nonionic surfactants, and ampholytic surfactants.
  • nonionic surfactants are preferable, and examples thereof include polyoxyethylene alkyl ethers, alkylphenol ⁇ ethylene oxide adducts, and higher alcohol phosphoric acid esters.
  • the organosilicon compound is not limited so far as it is a compound having at least an Si-O-R bond and/or an Si-N-R bond and/or an Si-R bond.
  • the organosilicon compound is in the form of a monomer, a lowly condensed product, a polymer, etc. Examples thereof include organosilane compounds such as methyltriethoxysilane; and dimethylsilicone oil, polyorganosiloxane, or silicone resin compositions containing the same.
  • the pyroelectric substance is not limited so far as it has pyroelectricity.
  • Examples thereof include tourmaline, hemimorphic ores, and pyroelectric ores.
  • Tourmaline or achroite which is a kind of tourmaline is especially preferable.
  • Examples of the tourmaline include dravite, schorl, and elbaite.
  • the moisturizer is not limited so far as it is able to hold moisture.
  • Examples thereof include hyaluronic acid, collagen, glycerin, and urea.
  • the fertilizer component is not limited so far as it is a component containing at least one of three elements of nitrogen, phosphorus and potassium. Examples thereof include a bone powder, urea, ammonium sulfate, calcium perphosphate, potassium chloride, and calcium sulfate.
  • the hydrophobic polymer compound is not limited so far as it is a polymer compound having a contact angle with water of 40° or more, preferably 50° or more, and more preferably 60° or more in order to improve the draining in the composition.
  • the shape of the hydrophobic polymer compound is not limited, and examples thereof include powdery, particulate, granular, and tablet shapes.
  • Examples of the hydrophobic polymer compound include polyolefins such as polyethylene and polypropylene, polyesters, and polyamides.
  • heat generating aid examples include metal powders, metal salts, and metal oxides such as Cu, Mn, CuCl 2 , FeCl 2 , manganese dioxide, cupric oxide, triiron tetroxide, and mixtures thereof.
  • the acidic substance may be any of an inorganic acid, an organic acid, or an acidic salt.
  • examples thereof include hydrochloric acid, sulfuric acid, nitric acid, acetic acid, oxalic acid, citric acid, malic acid, maleic acid, chloroacetic acid, iron chloride, iron sulfate, iron oxalate, iron citrate, aluminum chloride, ammonium chloride, and hypochlorous acid.
  • the heat generating composition of the invention contains, as essential components, an iron powder, a carbon component, a reaction accelerator and water and may further contain at least one member selected from additional components consisting of a water retaining agent, a water absorptive polymer, a pH adjusting agent, a hydrogen formation inhibitor, an aggregate, a fibrous material, a functional substance, a surfactant, an organosilicon compound, a pyroelectric substance, a moisturizer, a fertilizer component, a hydrophobic polymer compound, a heat generating aid, a metal other than iron, a metal oxide other than iron oxide, an acidic substance, and a mixture thereof.
  • additional components consisting of a water retaining agent, a water absorptive polymer, a pH adjusting agent, a hydrogen formation inhibitor, an aggregate, a fibrous material, a functional substance, a surfactant, an organosilicon compound, a pyroelectric substance, a moisturizer, a fertilizer component, a hydrophobic poly
  • the heat generating composition of the invention contains, as essential components, an iron powder, a carbon component, a reaction accelerator and water, and its production process is one which can be put into practical use on an industrial scale.
  • a reaction mixture containing, as essential components, an iron powder, a reaction accelerator and water and having a water content of from 1 to 20 % by weight and a water mobility value showing a surplus water content of less than 0.01 is brought into contact with an oxidizing gas under circumstances at 0 °C or higher, a temperature rise of the reaction mixture is regulated at 1 °C or more within 10 minutes to produce a heat generating mixture, and the subject heat generating mixture is used as a raw material to form a heat generating composition.
  • a heat generating composition may be formed by subsequently further adjusting the water content, or by further adding a carbon component, etc. and adjusting the water content.
  • the contact treatment with an oxidizing gas within a short period of time by regulating the water content of the reaction mixture at a fixed amount or less, especially regulating the surplus water content of the reaction mixture at a fixed amount or less and carrying out an oxidizing contact treatment.
  • By specifying the surplus water content and performing the treatment within a short period of time adverse influences such as poor initial exothermic rising of the heat generating composition and shortening of the heat generation-retaining time can be avoided.
  • stirring or the like may not be achieved during the contact treatment with an oxidizing gas, when stirring or the like is achieved, the contact treatment with an oxidizing gas can be surely carried out.
  • the state of the reaction mixture or heat generating mixture at the time of the contact treatment with an oxidizing gas may be any of a standing state, a transfer state, or a fluidizing state by stirring, etc. and may be properly selected.
  • the circumstances at the time of mixing the respective components of the reaction mixture, the heat generating mixture or the heat generating composition and at the time of mixing at the time of adjusting the water content are not limited, and examples thereof include those in an oxidizing gas atmosphere and those in blowing of an oxidizing gas.
  • the "adjustment of the water content" as referred to herein means that after contact treating the heat generating mixture with an oxidizing gas, water or an aqueous solution of a reaction accelerator is added.
  • the amount of addition of water or an aqueous solution of a reaction accelerator is not limited, examples thereof include the addition of a weight corresponding to a reduced weight by the contact treatment and the addition of a weight such that a desired water mobility value is obtained. Whether or nor the adjustment of the water content is introduced may be properly determined depending upon the utility.
  • the heat generating composition of the invention contains, as essential components, an iron powder, a carbon component, a reaction accelerator and water and is started from a mixture obtained by contact treating a reaction mixture containing, as essential components, an iron powder, a reaction accelerator and water with an oxidizing gas.
  • the heat generating composition of the invention is usually one obtained by adjusting the water content of a heat generating mixture and is a heat generating composition which is satisfactory in the exothermic rising, has a suitable amount of surplus water and has excellent moldability. Furthermore, it is possible to produce a heat generating body which can become promptly warm at the time of use. Accordingly, at least the iron powder further including the carbon component has a history of oxidation by the contact treatment with an oxidizing gas, and it is thought that this is deeply related to excellent exothermic rising properties, exothermic endurance and excellent moldability.
  • the resistance to compression is preferably 80 % or more, more preferably 85 % or more, and further preferably 90 % or more.
  • the amount of addition of the carbon component (for example, active carbon) in the heat generating composition can be reduced by, for example, 20 % or more. By reducing the amount of addition of the carbon component, the costs are lowered.
  • the carbon component for example, active carbon
  • the amount of the carbon component is from 1.0 to 50 parts by weight; the amount of the reaction accelerator is from 1.0 to 5.0 parts by weight; and the amount of water is from 5 to 60 parts by weight, respectively based on 100 parts by weight of the iron powder (in the case of an iron powder having an iron oxide film, an iron powder as reduced in terms of an iron component amount in the reaction mixture).
  • the amount of the water retaining agent is from 0.01 to 10 parts by weight; the amount of the water absorptive polymer is from 0.01 to 20 parts by weight; the amount of the pH adjusting agent is from 0.01 to 5 parts by weight; the amount of the hydrogen formation inhibitor is from 0.01 to 12 parts by weight; the amount of each of the aggregate, the fibrous material and the functional substance is from 0.01 to 10 parts by weight; the amount of the surfactant is from 0.01 to 5 parts by weight; the amount of each of the organosilicon compound, the pyroelectric substance, the moisturizer, the fertilizer component, the hydrophobic polymer compound, the anti-foaming agent, the heat generating aid, the metal other than iron and the metal oxide other than iron oxide is from 0.01 to 10 parts by weight; and the amount of the acidic substance is from 0.001 to 1 parts by weight, respectively.
  • a heat generating composition having excellent exothermic rising properties, excellent hydrophilicity and excellent moldability.
  • a heat generating composition having both remarkably excellent moldability and exothermic characteristics is obtained. Since the heat generating composition as produced by the production process of the invention is remarkably improved with respect to exothermic rising properties, the amount of addition of a carbon component such as active carbon in the heat generating composition can be reduced by, for example, 20 % or more, leading to contribution to a reduction in costs. Furthermore, since the hydrophilicity is remarkably improved, the moldability with a mold is remarkably improved.
  • a marketed heat generating body in which a heat generating composition is accommodated in an accommodating bag is provided on the assumption that it is accommodated in an outer bag which is an air-impermeable accommodating bag and is storable over a long period of time, it is preferred to use a heat generating composition containing a hydrogen formation inhibitor. Since the heat generating composition which has passed through the contact treatment with an oxidizing gas is an active composition, it is important that the heat generating composition contains a hydrogen formation inhibitor. Also, this efficacy is further strengthened by using a pH adjusting agent together.
  • the heat generating composition having a water mobility value of less than 0.01 may contain a flocculant aid, a flocculant, an agglomeration aid, a dry binder, a dry binding agent, a dry binding material, a sticky raw material, a thickener, an excipient, or a water-soluble polymer in an amount ranging from 0.01 to 3 parts by weight respectively.
  • the "flocculant aid” as referred to herein is a flocculant aid as described in Japanese Patent No. 3,161,605 ( JP-T-11-508314 ) such as gelatin, natural gum, and corn syrup.
  • the "flocculant” as referred to herein is a flocculant as described in JP-T-2002-514104 such as corn syrup and maltitol syrup.
  • the "agglomeration aid” as referred to herein is an agglomeration aid as described in JP-T-2001-507593 such as corn syrup.
  • the "dry binder” as referred to herein is a dry binder as described in JP-T-2002-514104 such as microcrystalline cellulose, maltodextrin, and mixtures thereof.
  • the "dry binding agent” as referred to herein is a dry binding agent as described in JP-T-2001-507593 such as maltodextrin and sprayed lactose.
  • the "dry binding material” as referred to herein is a dry binding material as described in JP-T-11-508314 such as microcrystalline cellulose, maltodextrin, and mixtures thereof.
  • the "sticky raw material” or the “binder” as referred to herein is a sticky raw material or binder as described in JP-A-4-293989 such as water glass, polyvinyl alcohol (PVA), and carboxymethyl cellulose (CMC).
  • the “thickener” as referred to herein is a thickener as described in JP-A-6-343658 such as corn starch and potato starch.
  • excipient as referred to herein is an excipient as described in JP-A-7-194641 such as ⁇ -starch and sodium alginate.
  • water-soluble polymer as referred to herein, the water-soluble polymer in the adhesive layer can be used.
  • the particle size of a solid component constituting each of the reaction mixture, the heat generating mixture and the heat generating composition is not limited so far as the heat generating composition has moldability. In the case where any one of the sizes (length, width and height) of the heat generating composition molded body is made small, it is preferred to make the particle size of the solid component small.
  • a maximum particle size of the water-insoluble solid component exclusive of the reaction accelerator and water in the components constituting the heat generating composition or the like is preferably not more than 2.5 mm, more preferably not more than 930 ⁇ m, further preferably not more than 500 ⁇ m, still further preferably not more than 300 ⁇ m, even further preferably not more than 250 ⁇ m, and even still further preferably not more than 200 ⁇ m.
  • 80 % or more of the particle size of the solid component is preferably not more than 500 ⁇ m, more preferably not more than 300 ⁇ m, further preferably not more than 250 ⁇ m, still further preferably not more than 150 ⁇ m, and even further preferably not more than 100 ⁇ m.
  • the heat generating composition can be classified into a powder or granulate heat generating composition (having a water mobility value of less than 0.01), a moldable heat generating composition (having a water mobility value of from 0.01 to 20), and a sherbet-like heat generating composition (having a water mobility value exceeding 20 but not more than 50) depending upon the state of adjustment of the water content or the amount of surplus water.
  • the heat generating composition as classified depending upon the water mobility value is as above.
  • the water-soluble polymer compound is not limited so far as it is a water-soluble organic polymer.
  • examples thereof include single kinds or combinations of two or more kinds such as starch, gum arabic, methyl cellulose (MC), carboxymethyl cellulose (CMC), sodium carboxymethyl cellulose, polyvinyl alcohol, gelatin, polyacrylic acid, polyacrylic acid salts, polyacrylic acid partially neutralized products, polyvinylpyrrolidone, and N-vinylacetamide copolymers.
  • the heat generating body of the invention is a heat generating body in which a heat generating composition having satisfactory exothermic rising properties is accommodated in an accommodating bag in which at least a part thereof is air permeable.
  • a preferred heat generating body of the invention may form an exothermic part by one section or may form an exothermic part from a sectional exothermic part composed of two or more plural sections as disposed at intervals.
  • the heat generating body of the invention is sealed in an outer bag which is an air-impermeable accommodating bag.
  • the air-permeable accommodating bag which is used in the invention is not particularly limited with respect to the material quality and construction of a packaging material so far as it is able to hold the heat generating composition therein, is free from leakage of the raw materials during the use of the heat generating body, has a strength such that there is no possibility of breakage of the bag, and has air permeability necessary for the heat generation.
  • air permeability of the accommodating bag can be provided in a part or on one surface or both surfaces of the bag, and the air-permeable surface can be constituted of an air-permeable packing material. In the case where the both surfaces are air permeable, the air permeability of one surface may differ from that of the other surface.
  • the accommodating bag of the invention comprises a substrate and a covering material, and an underlay material may further be provided between the substrate and the covering material.
  • the air-permeable accommodating bag of the invention is not particularly limited with respect to the material quality and construction of a packaging material so far as it is able to hold the mixture therein, is free from leakage of the raw materials during the use of the heat generating body, has a strength such that there is no possibility of breakage of the bag, and has air permeability necessary for the heat generation. Furthermore, with respect to the air permeability of the accommodating bag, an air-permeable packaging material can be used in a part or on one surface or both surfaces of the bag.
  • the air permeability is not limited so far as the heat generation can be kept.
  • the air permeability is usually from 50 to 10, 000 g/m 2 /24 hr, preferably from 50 to 5, 000 g/m 2 /24 hr, more preferably from 70 to 5, 000 g/m 2 /24 hr, further preferably from 700 to 1,000 g/m 2 /24 hr, and still further preferably from 80 to 800 g/m 2 /24 hr in terms of a moisture permeability by the Lyssy method.
  • the term "g/m 2 /24 hr" has the same meaning as "g/(m 2 /24 hr)".
  • the moisture permeability is less than 50, the heat value is small and a sufficient thermal effect is not obtained, and therefore, such is not preferable.
  • the exothermic temperature is high so that a problem in safety may possibly be generated, and therefore, such is not preferable.
  • the moisture permeability exceeds 10,000 g/m 2 /24 hr depending upon the utility, or even in use at a moisture permeability closed to the open system, according to circumstances.
  • the air-permeable raw material constituting the air-permeable accommodating bag is not particularly limited so far as it can be formed into a film and is able to realize air permeability by stretching and/or extraction with a soluble filling agent or a method such as perforation by an extra fine needle.
  • Examples thereof include air-permeable films (for example, porous films and perforated films); materials having air permeability by themselves (for example, papers and non-woven fabrics) ; materials prepared by laminating at least one of papers and air-permeable films and non-woven fabrics so as to have air permeability; materials prepared by providing an air-impermeable packaging material comprising a non-woven fabric having a polyethylene film laminated thereon with fine pores by using a needle, etc.
  • porous film can be properly selected among porous films obtained by stretching a film made of a polyolefin based resin (for example, polyethylene, linear low density polyethylene, and polypropylene) or a fluorine based resin (for example, polytetrafluoroethylene) and a filler.
  • a polyolefin based resin for example, polyethylene, linear low density polyethylene, and polypropylene
  • fluorine based resin for example, polytetrafluoroethylene
  • the "perforated film” as referred to herein is a film prepared by providing an air-impermeable film (for example, polyethylene films) with fine pores by using a needle so as to have air permeability.
  • the packaging material of the accommodating bag may be of a single-layered structure or a multilayered structure. Its structure is not limited, and the multilayered structure is enumerated as follows.
  • the substrate is made of layer A/layer B, layer A/layer B/layer C, or layer A/layer B/layer C/layer D; and the covering material is made of layer F/layer G, layer E/layer F/layer G, or layer F/layer H/layer G.
  • the layer A include thermoplastic resin films (for example, polyethylene), heat seal layers (for example, polyethylene, EVA, and a mixture of EVA and polyethylene), and water absorptive papers.
  • Examples of the layer B include non-woven fabrics of a thermoplastic resin (for example, nylons), non-water absorptive papers, water absorptive papers, thermoplastic resin films (for example, polyethylene films, polypropylene films, polyester films, and polyamide (for example, nylons) films), wicks (for example, non-water absorptive papers and water absorptive papers).
  • Examples of the layer C include adhesive layers, non-water absorptive papers, water absorptive papers, thermoplastic resin films (for example, polyethylene), non-slip layers, and non-woven fabrics of a thermoplastic resin (for example, polyesters and nylons).
  • Examples of the layer D include separators, thermoplastic resin films (for example, polyethylene), and non-woven fabrics.
  • Examples of the layer E include heat seal layers.
  • Examples of the layer F include porous films or perforated films made of a thermoplastic resin (for example, polyethylene), films made of a thermoplastic resin (for example, polyethylene), non-water absorptive papers, and water absorptive papers.
  • Examples of the layer G include non-woven fabrics of a thermoplastic resin (for example, polyesters and nylons).
  • Examples of the layer H include non-water absorptive papers and water absorptive papers.
  • the substrate or covering material examples include polyethylene-made heat seal layer/polypropylene film, EVA-made heat seal layer/polypropylene film, EVA-made heat seal layer/polypropylene film/adhesive layer/separator, EVA-made heat seal layer/polyethylene film/nylon non-woven fabric, polyethylene-made heat seal layer/polypropylene film/polypropylene non-woven fabric, non-woven fabric/porous film, non-woven fabric/paper or perforated (provided by a needle or laser) film/porous film, non-woven fabric/paper or porous film/perforated (provided by a needle or laser) film, and non-woven fabric/paper or porous film/non-woven fabric.
  • a method for laminating the respective layers is not limited.
  • the respective layers may be directly laminated; the respective layers may be laminated via an air-permeable adhesive layer or a laminating agent layer; and the respective layers may be laminated by hot melt extrusion or the like.
  • polyethylene produced by using a metallocene catalyst is also included in the polyethylene.
  • the heat generating body may be accommodated in an outer bag which is an air-impermeable accommodating bag, stored and transported.
  • the outer bag is not limited so far as it is air-impermeable and may be made of a laminate. Examples thereof include air-impermeable raw materials such as nylon, polyester and polypropylene films which are subjected to a moisture-proof treatment with OPP, CPP, polyvinylidene chloride, metal oxides (including semiconductors) such as aluminum oxide and silicon oxide, etc., aluminum foils, and aluminum-deposited plastic films.
  • the air-impermeable raw material examples include polyethylene, polypropylene, cellophane, polyesters, polyamides, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, polyurethane, polystyrene, ethylene-vinyl acetate copolymers, polycarbonates, and hydrochlorinated rubber.
  • polyolefin based resin-made raw materials are preferable because a uniform air-permeable film is obtainable by stretching, etc.
  • this polyolefin based resin include homopolymers (for example, polyethylene, polypropylene, and polybutadiene) or copolymers or blended polymers thereof.
  • examples of a film having high air impermeability include films in which a single layer or multiple layers made of a metal including semiconductors or a compound thereof are provided on an air-impermeable raw material film.
  • the metal including semiconductors include silicon, aluminum, titanium, tin, indium, and alloys or mixtures of these metals.
  • the metal compound including semiconductors include oxides, nitrides and oxynitrides of the foregoing metals or alloys or mixtures.
  • Examples of the layer include a silicon oxide layer, an aluminum oxide layer, a silicon oxynitride layer, and layers obtained by laminating arbitrary layers thereof.
  • thermoelectric layer obtained by laminating a stretched polyolefin film (for example, a biaxially stretched polypropylene film) on the foregoing layer.
  • a stretched polyolefin film for example, a biaxially stretched polypropylene film
  • the heat generating body which is accommodated in an outer bag include a heat generating body in which a produced heat generating body is sealed between two air-impermeable films or sheets.
  • the raw material constituting the substrate, the covering material or the underlay material is not limited so far as it functions as an accommodating bag of the heat generating composition, and any materials which are hitherto used in air-permeable accommodating bags of heat generating bodies are useful. Examples thereof include air-impermeable raw materials, air-permeable raw materials, water absorptive raw materials (for example, papers and rayon), non-water absorptive raw materials, stretchable raw materials, non-stretchable raw materials, foamed raw materials, and heat sealable raw materials.
  • the raw material may be properly used in a desired shape such as a film, a sheet, a non-woven fabric, a woven fabric, and a composite thereof depending upon the intended utility.
  • the non-water absorptive raw material is not limited so far as it is non-water absorptive.
  • examples thereof include films, sheets and coatings made of a synthetic resin (for example, polyethylene, polypropylene, nylons, polyacrylates, polyesters, polyvinyl alcohol, and polyurethane) or the foregoing hydrophobic polymer.
  • the stretchable packaging material is not particularly limited so far as it is stretchable. That is, it is only required that the stretchable packaging material is stretchable as a whole.
  • the stretchable packaging material may be formed of a single material or a composite material among stretchable substrates or a combination of a stretchable substrate and a non-stretchable substrate.
  • stretchable packaging material examples include fabrics, films, spandex yarns, yarns, strands, flat plates, ribbons, slit films, foamed bodies or non-woven fabrics constituted of a single material (for example, natural rubbers, synthetic rubbers, elastomers, and stretchable shape memory polymers) or a mixed material, a blended material or a combination thereof with a non-stretchable raw material, and composite stretchable materials made of a laminate among such stretchable raw materials or such a stretchable raw material and a non-stretchable material.
  • a single material for example, natural rubbers, synthetic rubbers, elastomers, and stretchable shape memory polymers
  • fibers constituting the woven fabric natural fibers, regenerated fibers using a natural raw material such as viscose fibers, semi-synthetic fibers, synthetic fibers, and mixtures of two or more kinds thereof can be used. These fibers can also be used as a fibrous material.
  • the non-woven fabric is not limited so far as it is a cloth-like sheet as produced by welding a fiber by tanglement or bonding by thermal, chemical, physical or mechanical means or other means, such as heat, an adhesive, and high-pressure stream of water.
  • Materials having one kind or a combination of two or more kinds of stretchable, non-stretchable, water absorptive, non-water absorptive, heat sealable, and non-heat sealable properties are employable.
  • Examples thereof include vegetable fibers (for example, rayon, nylons (polyamides), polyesters, polyacrylates, polypropylene, vinylon, polyethylene, polyurethane, cupra, cotton, cellulose, and pulp), single fibers or composite fibers or mixed fibers made of a synthetic pulp and a thermoplastic polymer substance, and mixtures thereof.
  • Single non-woven fabrics or laminates of mixed or accumulated fiber layers of such a fiber are used. Short fiber non-woven fabrics, long fiber non-woven fabrics, and continuous filament non-woven fabrics can also be used.
  • dry non-woven fabrics, wet non-woven fabrics, spunbonds, spunlaces, and the like can be used.
  • the stretchable non-woven fabric is not limited so far as it is stretchable.
  • examples thereof include non-woven fabrics of an elastomer based rubber based fiber, entangled fabrics of a polyolefin based or polyester based crimped fiber, and stretchable non-woven fabrics or polyurethane based non-woven fabrics produced by using a binder or by a hot melt measure.
  • Non-woven fabrics made of a composite fiber of a core-sheath structure are also employable.
  • a basis weight of the non-woven fabric is not limited but is preferably from 10 to 200 g/m 2 .
  • the paper is not limited so far as it is water absorptive and is usually used.
  • Examples thereof include papers and cardboards.
  • Examples include one kind or laminates of two or more kinds of thin papers (for example, blotting paper, tissue paper, and crepe paper), packaging papers (for example, craft paper), miscellaneous papers (for example, card paper), corrugated cardboard, inner wicks for corrugated cardboard (for example, pulp wick and special wick), liners for corrugated cardboard (for example, kraft and jute), cardboards (for example, coated cardboard), and construction papers (for example, gypsum board original paper).
  • thin papers for example, blotting paper, tissue paper, and crepe paper
  • packaging papers for example, craft paper
  • miscellaneous papers for example, card paper
  • corrugated cardboard inner wicks for corrugated cardboard (for example, pulp wick and special wick)
  • liners for corrugated cardboard for example, kraft and jute
  • cardboards for example, coated cardboard
  • construction papers for
  • the non-water absorptive paper is not limited so far as it is non-water absorptive.
  • Examples thereof include papers obtained by subjecting the foregoing paper or cardboard to a non-water absorptive treatment.
  • Examples include papers resulting from a non-water absorptive treatment by impregnation or coating with an oil or a synthetic resin and papers resulting from laminating a non-water absorptive raw material such as a polyethylene film.
  • the paper and the non-water absorptive paper may be subjected to waterproof processing or may be provided with perforations using laser, a needle, or the like so as to adjust or provide air permeability.
  • foamed raw material examples include foamed bodies such as sheets formed of at least one kind selected from foamed polyurethane, foamed polystyrene, foamed ABS resins, foamed polyvinyl chloride, foamed polyethylene, and foamed polypropylene.
  • the heat sealable raw material may be a single raw material or a composite raw material having a heat seal layer and is not limited so far as at least a part thereof can be welded by heating.
  • the heat sealable raw materials or a hot melt based adhesive constituting a heat seal layer include polyolefins (for example, polyethylene and polypropylene) or olefin copolymer resins, ethylene based hot melt resins such as ethylene-acrylic acid ester copolymer resins (for example, ethylene-methyl methacrylate copolymers, ethylene-methyl methacrylic acid-acrylic acid ester copolymers, ethylene- ⁇ -olefin copolymers, ethylene-vinyl acetate copolymer resins, and ethylene-isobutyl acrylate copolymer resins), polyamide based hot melt resins, polyester based hot melt resins, butyral based hot melt resins, cellulose derivative based hot melt resins, polymethyl methacrylate
  • the hot melt based resins or films or sheets thereof can be compounded with various additives such as antioxidants.
  • various additives such as antioxidants.
  • low density polyethylene, polyethylene obtained by using a metallocene catalyst, and ethylene- ⁇ -olefin copolymers are useful.
  • the ⁇ -olefin is not limited so far as it is a monomer having a double bond in the terminal thereof. Examples thereof include polypropylene, 1-butene, 1-heptane, 1-hexene, 1-octene, and 4-methyl-1-ptentene.
  • biodegradable raw materials can be used.
  • the heat generating composition may be subjected to a compression treatment.
  • a molded body prepared by appropriately compressing the heat generating composition molded body of the invention under pressure is markedly improved in shape holding properties. For example, even when a perforated film which is difficult with respect to the pressure adjustment is used as a raw material of the air-permeable part in place of the porous film, or even when an inner pressure of the accommodating bag becomes equal to or more than the outer pressure, shape collapse hardly occurs so that a perforated film can be used.
  • a heat generating composition molded body prepared by compression treating the heat generating composition of the invention is a non-elastic body.
  • the resistance to compression of the heat generating composition is preferably 80 % or more, more preferably 85 % or more, and further preferably 90 % or more, or it may exceed 100 %.
  • the exothermic part for the purpose of containing a magnetic substance in at least a part thereof or one sectional exothermic part to improve the blood circulation or stiff shoulders due to a magnetic effect, it is also possible to accommodate therein a magnetic substance such as a magnet.
  • a magnetic substance such as a magnet.
  • the magnetic substance is accommodated in at least one sectional region of the sectional regions.
  • the separator may be provided with a notch such as a slit.
  • the adhesive layer is preferably non-transferable.
  • At least one member selected from additional components consisting of a moisturizer, a functional substance, an aggregate, a pyroelectric substance, a magnetic body, and a mixture thereof may be contained in or carried on at least one member selected from the substrate, the underlay material, the covering material, and the adhesive layer.
  • the content of such a material is not particularly limited. However, from the viewpoints of medicinal effect, economy, adhesive force, and the like, it is preferably from 0.01 to 25 parts by weight, and more preferably from 0.5 to 15 parts by weight based on 100 parts by weight of the adhesive.
  • a hot melt based adhesive may be provided between the hydrophilic adhesive layer and the substrate or the covering material. Furthermore, in the case of providing the hydrophilic adhesive in the heat generating body, though there is no limitation, it is preferred to provide the hydrophilic adhesive in the heat generating body after the seal treatment of the heat generating body.
  • the exothermic part may be formed by one section.
  • sectional exothermic parts may be formed by disposing and fixing two or more plural sections at intervals, and an exothermic part may be formed from a gathering of these sectional exothermic parts and provided for the exothermic part.
  • the size of the heat generating composition molded body on the substrate is not larger than that of the sectional exothermic part, and the periphery of the heat generating composition molded body is heat sealed, thereby constituting the sectional exothermic part and the exothermic part.
  • a capacity of the sectional exothermic part or the exothermic part is composed of a capacity of the filling heat generating composition or a capacity of the heat generating composition molded body and a spacial capacity surrounding it.
  • a capacity ratio of the capacity of the filling heat generating composition or the heat generating composition molded body to the capacity of the sectional exothermic part or the capacity of the exothermic part is usually from about 0. 3 to about 1.0, preferably from about 0.35 to about 1.0, more preferably from about 0.5 to about 1.0, further preferably from about 0.7 to about 1.0, still further preferably from about 0.8 to about 1.0, and even further preferably from about 0.9 to about 1.0.
  • the sectional exothermic part when its size is small as far as possible, it is possible to make the heat generating body flexible as a whole.
  • one side of a sectional exothermic part which is constituted of at least two sides having a different length from each other is short as far as possible.
  • a sectional exothermic part which is constituted of the same side as in a square or the like or one diameter as in a circle or the like it is preferable that the longest length is short as far as possible.
  • the sectional exothermic part accommodates therein a heat generating composition or a heat generating composition molded body as sectioned by a sectioning part which is a seal part.
  • its maximum width is usually from 0.5 to 60 mm, preferably from 0.5 to 50 mm, more preferably from 1 to 50 mm, further preferably from 3 to 50 mm, still further preferably 3 to 30 mm, even further preferably from 5 to 20 mm, even still further preferably from 5 to 15 mm, and most preferably from 5 to 10 mm.
  • its maximum height is usually from 0.1 to 30 mm, preferably from 0.1 to 10 mm, more preferably from 0.3 to 10 mm, further preferably from 1 to 10 mm, and still further preferably from 2 to 10 mm.
  • its longest length is usually from 5 to 300 mm, preferably from 5 to 200 mm, more preferably from 5 to 100 mm, further preferably from 20 to 150 mm, and still further preferably from 30 to 100 mm.
  • a capacity of the sectional exothermic part or a volume of the heat generating composition molded body is usually from 0.015 to 500 cm 3 , preferably from 0.04 to 30 cm 3 , more preferably from 0.1 to 30 cm 3 , further preferably from 1 to 30 cm 3 , and still further preferably from 3 to 20 cm 3 .
  • a volume ratio of the volume of the heat generating composition molded body which is an occupying region of the heat generating composition molded body to the capacity of the sectional exothermic part which is an accommodating region of the heat generating composition is usually from 0. 6 to 1, preferably from 0.7 to 1, more preferably from 0.8 to 1, and further preferably from 0.9 to 1.0.
  • a width of the sectioned part which is a space between the sectional exothermic parts is not limited so far as sectioning can be achieved.
  • the heat generating composition molded body or the sectional exothermic part may have any shape.
  • the shape may be a planar shape, and examples thereof include a circular shape, an elliptical shape, a polygonal shape, a star shape, and a flower shape.
  • the shape may be a three-dimensional shape, and examples thereof include a polygonal pyramidal shape, a conical shape, a frustum shape, a spherical shape, a parallelepiped shape, a cylindrical shape, a semi-pillar shape, a semicylindroid shape, a semicylidrical shape, a pillar shape, and a cylindroid shape.
  • the corner may be rounded, thereby processing the corner in a curvilinear or curved state, or the central part may be provided with a concave.
  • volume of the heat generating composition molded body of the invention as referred to herein means a volume of the heat generating composition molded body or compressed heat generating composition molded body.
  • volume of the sectional exothermic part as referred to herein means an internal capacity of the sectional exothermic part having a heat generating composition molded body accommodated therein.
  • the height of the central part may become low step by step toward the surroundings, namely a height gradation may be provided, or a reverse height gradation may be provided.
  • the size of the heat generating composition molded body is first determined, and the size of the sectional exothermic part is then determined.
  • the accommodating bag, the outer bag (accommodating bag of the heat generating body), and the like, packaging materials or the like constituting the same are sealed in the sectioned part or its surroundings.
  • Its seal is not limited but is properly selected depending upon the desire.
  • sealing is carried out in a point-like (missing line) state or entirely by compression seal (adhesive seal), warm compression seal (adhesive seal), bonding seal, heat bonding seal, heat melt seal (heat seal), etc. by means of pressurizing, warming, heating or a combination thereof via an adhesive layer and/or a bonding agent layer and/or a heat seal layer. Selection of any one or a combination of these methods may be made depending upon the desire. In this way, it is possible to seal and form a sectional exothermic part, an inner bag (accommodating bag), an outer bag, etc. Sewing processing can also be employed as one of seal means.
  • a width of the periphery in the substrate for forming an accommodating bag such as a substrate and a covering material or in the seal part of the sectioned part can be properly determined. It is usually not more than 50 mm, preferably from 1 to 30 mm, and more preferably from 3 to 20 mm.
  • a cutting line such as a perforation can be provided as the need arises.
  • This perforation may be provided to a degree such that bending properties are improved or may be provided to a degree such that cutting by hand is possible, for example, a degree for forming a heat generating body of a size adaptive with a place for application of a human body, or the like. This degree is not limited but is determined depending upon the desire.
  • the size of the heat generating body and the size and number of the sectional exothermic parts may be properly set up.
  • the sectioned part can be formed in arbitrary directions such as a length or width direction, length and width directions, and an oblique direction.
  • At least a part of the surface of the heat generating composition may be covered by an air-permeable adhesive layer of a network-like polymer, etc.
  • an underlay material such as non-woven fabrics may be provided between the air-permeable adhesive layer and the covering material.
  • the entire surface or a partial surface of at least one kind of the heat generating composition molded body, the substrate, the covering material and the underlay material may be subjected to a pressurizing treatment or the like or may be formed with irregularities. In this way, transfer of the laminate between the substrate and the covering material may be prevented.
  • the "perforation" as referred to in the invention includes one which is intermittently cut for the purpose of improving flexural properties of the sectioned part and one which is intermittently cut such that cutting by hand is possible. Its degree, length and aperture are not limited but are determined depending upon the desire.
  • the perforation may be provided in all sectioned parts or may be partially provided.
  • the shape is not particularly limited, and examples thereof include a circle, an ellipse, a rectangle, a square, and a cut line (linear shape).
  • a circular hole having an aperture of from ⁇ 10 to 1,200 ⁇ m can be enumerated.
  • the aperture of the hole is more preferably from ⁇ 20 to 500 ⁇ m. It is preferable that the holes are positioned lined up in the length and width. Furthermore, a shortest space between outer peripheries of the adjacent holes in the length and width is not limited so far as it is satisfactory with flexural properties and possibility of cutting by hand.
  • the shortest space is preferably from 10 to 2,000 ⁇ m, more preferably from 10 to 1,500 ⁇ m, further preferably from 20 to 1,000 ⁇ m, still further preferably from 20 to 500 ⁇ m, and even further preferably from 20 to 200 ⁇ m.
  • the cutting properties by hand are remarkably improved by a balance between the aperture of the hole and the shortest space of outer peripheries of the adjacent holes in the length and width.
  • the hole may be a cut line, and its length may be a length corresponding to the aperture or may be larger than the aperture.
  • a shortest space between ends of the adjacent cut lines in the length and width is corresponding to the shortest space between outer peripheries of the adjacent holes.
  • an aperture of the hole of from ⁇ 10 to 2, 000 ⁇ m is corresponding to a length of from 10 to 2,000 ⁇ m
  • a shortest space between outer peripheries of the adjacent holes in the length and width of from 10 to 2,000 ⁇ m is corresponding to a shortest space between ends of the adjacent cut lines in the length and width of from 10 to 2,000 ⁇ m.
  • a cut line since it becomes long in one direction, its length can be prolonged and may be from 10 to 50, 000 ⁇ m.
  • a shortest distance between the adjacent cut lines in the length and width may be from 1 to 5,000 ⁇ m.
  • the fixing means is not limited so far as it has capability for fixing a thermal packaging body for joint surroundings or a material having an exothermic part to a prescribed part.
  • an adhesive layer, a hook and eye, a hook and button, a hook and loop fastener such as Velcro, a magnet, a band, a string, and combination thereof can be arbitrarily used.
  • fixing means for adjustment may be further constructed by a combination of a hook and loop fastener and an adhesive layer.
  • the "hook and loop fastener” as referred to herein has a fastening function by a combination of a loop as a female fastener with a male fastener capable of fastening the female fastener thereto, which is known as trade names such as Magic Tape (a registered trademark), Magic Fastener (a registered trademark), Velcro Fastener, and Hook and Loop Tape.
  • a loop function examples include non-woven fabrics and woven fabrics of napped or hole-containing yarns.
  • Such a material having a loop function female fastener function
  • the hook member which is the male fastener member is not particularly limited, examples thereof include hook members formed of a polyolefin based resin (for example, polyethylene and polypropylene), a polyamide, a polyester, etc.
  • the shape of the hook is not particularly limited, a hook having a cross-sectional shape such as an I type, an inverted L type, an inverted J type, and a so-called mushroom type is preferable because it is easily hooked by the loop and does not give an extreme stimulus to the skin.
  • the hook may be adhered to the entire area of a fastening tape, and only the hook may be used as a fastening tape while omitting a tape substrate.
  • the adhesive layer may contain at least one member selected from additional components consisting of a water retaining agent, a water absorptive polymer, a pH adjusting agent, a surfactant, an organosilicon compound, a hydrophobic polymer compound, a pyroelectric substance, an antioxidant, an aggregate, a fibrous material, a moisturizer, a functional substance, and a mixture thereof.
  • the adhesive of the invention is classified into a non-hydrophilic adhesive, a mixed adhesive, and a hydrophilic adhesive (for example, a gel).
  • the adhesive constituting the adhesive layer is not limited so far as it has an adhesive strength necessary for adhering to the skin or clothes.
  • Adhesives of every form such as a solvent based adhesive, an aqueous adhesive, an emulsion type adhesive, a hot melt type adhesive, a reactive adhesive, a pressure-sensitive adhesive, a non-hydrophilic adhesive, and a hydrophilic adhesive are employable.
  • the adhesive layer includes one layer of a non-hydrophilic adhesive constituted of the non-hydrophilic adhesive and non-hydrophilic adhesive layers constituted of the non-hydrophilic adhesive. It is to be noted that a material whose water absorption properties are improving by containing a water absorptive polymer or a water retaining agent in the non-hydrophilic adhesive layer is dealt as the non-hydrophilic adhesive layer.
  • a hot melt based adhesive may be provided between the hydrophilic adhesive layer and a substrate or a covering material.
  • a hydrophilic adhesive layer may be provided in the thermal packaging body for joint surroundings.
  • the adhesive layer may or may not have air permeability and may be properly selected depending upon the utility. With respect to the air permeability, the adhesive layer may be air-permeable as a whole. Examples thereof include an adhesive layer having air permeability as a whole of a region in which an adhesive is partially present and a portion where no adhesive is present is partially present.
  • examples of a method for keeping its air permeability include a method in which an adhesive layer is partially laminated by printing or transferring an adhesive, thereby forming a non-laminated part as an air-permeable part; a method in which an adhesive is transferred in one direction while drawing a circle in a filament-like form or properly moved in the two-dimensional directions by transferring in a zigzag manner, whereby a space of the filament-like adhesive keeps air permeability or moisture permeability or the adhesive is foamed; and a method for forming a layer by a melt blow system.
  • the adhesive which constitutes the non-hydrophilic adhesive layer examples include acrylic adhesives, polyvinyl acetate based adhesives (for example, vinyl acetate resin based emulsions and ethylene-vinyl acetate resin based holt melt adhesives), polyvinyl alcohol based adhesives, polyvinyl acetal based adhesives, vinyl chloride based adhesives, polyamide based adhesives, polyethylene based adhesives, cellulose based adhesives, chloroprene (neoprene) based adhesives, nitrile rubber based adhesives, polysulfide based adhesives, butyl rubber based adhesives, silicone rubber based adhesives, styrene based adhesives (for example, styrene based hot melt adhesives), rubber based adhesives, and silicone based adhesives.
  • polyvinyl acetate based adhesives for example, vinyl acetate resin based emulsions and ethylene-vinyl acetate resin based hol
  • rubber based adhesives, acrylic adhesives, and adhesives containing a hot melt based polymer substance for the reasons that they are high in the adhesive strength, are cheap, are good in long-term stability, and are small in reduction of the adhesive strength even by providing heat.
  • the adhesive may be compounded with other components such as tackifiers (for example, petroleum resins represented by rosins, chroman-indene resins, hydrogenated petroleum resins, maleic anhydride-modified rosins, rosin derivatives, and C-5 based petroleum resins), phenol based tackifiers (especially, tackifiers having an aniline point of not higher than 50 °C; for example, terpene phenol based resins, rosin phenol based resins, and alkylphenol based resins), softeners (for example, coconut oil, castor oil, olive oil, camellia oil, and liquid paraffin), softeners, anti-aging agents, fillers, aggregates, adhesion adjusting agents, adhesion modifiers, coloring agents, anti-foaming agents, thickeners, and modifiers, thereby improving performance such as an improvement in adhesion to nylon-made clothes and mixed yarn clothes.
  • tackifiers for example, petroleum resins represented by rosin
  • hot melt based adhesive examples include known hot melt based adhesives imparted with adhesion. Specific examples thereof include styrene based adhesives made of, as a base polymer, an A-B-A type block copolymer (for example, SIS, SBS, SEBS, and SIPS), vinyl chloride based adhesives made of, as a base polymer, a vinyl chloride resin, polyester based adhesives made of, as a base polymer, a polyester, polyamide based adhesives made of, as a base polymer, a polyamide, acrylic adhesives made of, as a base polymer, an acrylic resin, polyolefin based adhesives made of, as a base polymer, a polyolefin (for example, polyethylene, super low density polyethylene, polypropylene, ethylene- ⁇ -olefin copolymers, and ethylene-vinyl acetate copolymers), 1,2-polybutadiene based adhesives made of, as a base polymer, 1, 2-
  • Adhesive layers constituted of a foamed adhesive and adhesive layers constituted of a crosslinked adhesive can also be employed.
  • the non-aromatic hot melt based adhesive is not limited so far as it is made of, as a base polymer, a hot melt based adhesive not containing an aromatic ring. Examples thereof include olefin based hot melt based adhesives and acrylic hot melt based adhesives.
  • As the non-aromatic polymer which is the base polymer not containing an aromatic ring there are enumerated polymers or copolymers of an olefin or a diene. Examples thereof include olefin polymers.
  • the olefin polymer includes polymers or copolymers of ethylene or an ⁇ -olefin.
  • polymers resulting from adding a diene for example, butadiene and isoprene
  • a diene for example, butadiene and isoprene
  • the ⁇ -olefin is not limited so far as it is a monomer having a double bond in the terminal thereof. Examples thereof include propylene, butene, heptane, hexene, and octene.
  • the "aromatic hot melt based adhesive” as referred to herein is a hot melt based adhesive whose base polymer contains an aromatic ring. Examples thereof include styrene based hot melt based adhesives represented by A-B-A type block copolymers.
  • the A block is a non-elastic polymer block made of a monovinyl substituted aromatic compound A such as styrene and methylstyrene; and the B block is an elastic polymer block made of a conjugated diene such as butadiene and isoprene.
  • Specific examples thereof include a styrene-butadiene-styrene block copolymer (SBS), a styrene-isoprene-styrene block copolymer (SIS), and hydrogenated types thereof (for example, SEBS and SIPS), and mixtures thereof.
  • an adhesive layer obtained by further compounding a water absorptive polymer in the non-hydrophilic adhesive can be used.
  • the hydrophilic adhesive which constitutes the hydrophilic adhesive layer is not particularly limited so far as it contains a hydrophilic polymer or a water-soluble polymer as the major component, has adhesion and is hydrophilic as an adhesive.
  • hydrophilic polymers for example, polyacrylic acid
  • water-soluble polymers for example, poly(sodium acrylate) and polyvinylpyrrolidone
  • crosslinking agents for example, dry aluminum hydroxide and meta-silicic acid aluminic acid metal salts
  • softeners for example, glycerin and propylene glycol
  • higher hydrocarbons for example, soft liquid paraffin and polybutene
  • primary alcohol fatty acid esters for example, isopropyl myristate
  • silicon-containing compounds for example, silicone oil
  • fatty acid glycerin esters for example monoglycerides
  • oily components for example, vegetable oils such as olive oil
  • antiseptics for example, methyl p-hydroxybenzoate and propyl p-hydroxybenzoate
  • solubilizing agents for example, N-methyl-2-pyrrolidone
  • thickeners for example, carboxymethyl cellulose
  • surfactants for example, N-methyl-2-pyrrolidone
  • a temporary adhering seal part is formed via a sticky layer.
  • An adhesive which constitutes the sticky layer is a layer formed of a polymer composition which is tacky at the normal temperature and is not limited so far as it can be heat sealed after temporary adhesion. Furthermore, the foregoing adhesives of the sticky layer can be used as the adhesive which constitutes the sticky layer as used for temporary adhesion. Of these, non-hydrophilic adhesives are preferable. With respect to the adhesive constituting the adhesive layer, it is preferable that the adhesive is well compatible with a heat seal material constituting a heat seal and that a melting point of the base polymer of the adhesive is not higher than a melting point of the heat seal material.
  • Hot melt based adhesives are especially preferable for hot melt based bonding agents.
  • the heat seal material is an olefin based raw material
  • preferred examples thereof include olefin based adhesives.
  • a bonding layer for fixing the air permeability adjusting material is constituted of a bonding agent or an adhesive which is usually used.
  • an adhesive is useful, and the foregoing adhesives for constituting the adhesive layer can be used.
  • a method for providing a bonding layer is not limited so far as the air permeability adjusting material can be fixed.
  • the bonding layer may be entirely provided or partially or intermittently provided.
  • the shape examples include various shapes such as a network-like shape, a stripe-like shape, a dot-like shape, and strip-like shape.
  • an adhesive layer employed as the hydrophilic adhesive layer
  • transfer of water occurs via a packaging material present therebetween such as a substrate, thereby causing in-conveniences against the both.
  • the transfer of water occurs during the storage.
  • the packaging material present therebetween at least has a moisture permeability of not more than 2 g/m 2 /day in terms of a moisture permeability according to the Lyssy method.
  • the moisture permeability of a moisture-proof packaging material provided between the heat generating composition molded body and the hydrophilic adhesive layer is not limited so far as the transfer of water can be prevented within the range where the exothermic performance is not affected.
  • the moisture permeability according to the Lyssy method is usually not more than 2 g/m 2 /day, preferably not more than 1.
  • the moisture-proof packaging material can be used as a substrate or a covering material and may be laminated singly on a substrate, a covering material, or the like.
  • the moisture-proof packaging material is not limited so far as the transfer of water between the heat generating composition molded body and the hydrophilic adhesive layer can be prevented.
  • Examples thereof include metal vapor deposited films, vapor deposited films of a metal oxide, metal foil-laminated films, EVOH (ethylene/vinyl alcohol copolymer or ethylene/vinyl acetate copolymer saponified product) based films, biaxially stretched polyvinyl alcohol films, polyvinylidene chloride coated films, polyvinylidene chloride coated films obtained by coating polyvinylidene chloride on a substrate film (for example, polypropylene), metal foils such as an aluminum foil, air-impermeable packaging materials obtained by vapor depositing or sputtering a metal (for example, aluminum) on a polyester film substrate, and packaging laminates using a transparent barrier film of a structure in which silicon oxide or aluminum oxide is provided on a flexible plastic substrate.
  • a substrate film for example, polypropylene
  • metal foils such as an aluminum foil
  • air-impermeable packaging materials obtained by vapor depositing or sputtering a metal (for example, aluminum) on
  • the air-impermeable packaging materials which are used in the outer bag, etc. can also be used.
  • packaging materials such as moisture-proof packaging materials as described in JP-A-2002-200108 , the disclosures of which can be incorporated herein by reference, can be used.
  • the content of a reaction accelerator (for example, sodium chloride) or a substance having a water holding power (for example, a water absorptive polymer) in the heat generating composition may be adjusted within the range of from 10 to 40 % by weight, preferably from 15 to 40 % by weight, and more preferably from 15 to 30 % by weight based on the heat generating composition.
  • water-containing adhesives for example, hydrophilic adhesives and gels
  • adhesives which can be subjected to hot melt coating as described in JP-A-6-145050 and JP-A-6-199660
  • rubber based adhesives as described JP-A-10-279466 and JP-A-10-182408 , the disclosures of which are totally incorporated herein by reference, are useful.
  • the functional substance which is contained in the adhesive layer is not limited so far as it is a substance having any function.
  • aromatic compounds for example, menthol and benzaldehyde
  • vegetable extracts for example, mugwort extract
  • crude drugs for example, moxa
  • perfumes for example, lavender and rosemary
  • slimming agents for example, aminophylline and tea extract
  • analgesic drugs for example, indomethacin and dl -camphor
  • blood circulation promoters for example, acidic mucopolysaccharide and chamomile
  • swelling improvers for example, horse chestnut extract and flavone derivatives
  • fomentations for example, aqueous boric acid, physiological saline, and aqueous alcohols
  • fat-splitting components for example, jujube extract, caffeine, and tonalin
  • cosmetics for example, aloe extracts, vitamin preparations, hormone preparations, anti-histamines, and amino acids
  • antibacterial agents and sterilizers for example, carbolic acid derivatives, boric acid, iodine preparations, invert soaps
  • the percutaneously absorptive drug is not particularly limited so far as it has percutaneous absorption.
  • examples thereof include corticosteroids, anti-inflammatory drugs, hypertension drugs, anesthetics, hypnotic sedatives, tranquillizers, antibacterial substances, antifungal substances, skin stimulants, inflammation inhibitors, anti-epileptics, analgesics, antipyretics, anesthetics, mold inhibitors, antimicrobial antibiotics, vitamins, antiviral agents, swelling improvers, diuretics, antihypertensives, coronary vasodilators, anti-tussive expectorants, slimming agents, anti-histamines, antiarrhythmic agents, cardiotonics, adrenocortical hormones, blood circulation promoters, local anesthetics, fat-splitting components, and mixtures thereof.
  • the invention is limited thereto.
  • These drugs are used singly or in admixture of two or more kinds thereof as the need arises.
  • the content of such a functional substance is not particularly limited so far as it falls within the range where the effect of a medicine can be expected.
  • the content of the functional substance is preferably from 0.01 to 25 parts by weight, and more preferably from 0.5 to 15 parts by weight based on 100 parts by weight of the adhesive.
  • a method for providing the adhesive layer is not limited so far as a thermal packaging body for joint surroundings can be fixed.
  • the adhesive layer may be entirely provided or partially or intermittently provided. Examples of its shape include various shapes such as a network-like shape, a stripe-like shape, a dot-like shape, and strip-like shape.
  • At least one member or a part of the substrate, the covering material, the adhesive layer and the separator which constitute the heat generating body may be provided with at least one kind of characters, designs, symbols, numerals, patterns, photographs, pictures, and colored parts.
  • Each of the substrate, the covering material, the adhesive layer and the separator which constitute the heat generating body may be transparent, opaque, colored, non-colored, or the like. Furthermore, the layer constituting at least one layer of the layers constituting the respective materials and layers may have a colored part as colored different from other layers.
  • the heat generating body of the invention is able to give various shapes, thicknesses and temperature zones and therefore, can be used for various utilities such as use for indirect moxibustion, use for inside of shoes for feet, etc., use for a joint, facial esthetic use, use for eyes, use for a wet compress pack, use for a medical body warmer, use for a neck, use for a waist, use for a mask, use for a glove, use for hemorrhage, use for a shoulder, use for a cushion, use for an aroma, use for an abdomen, insecticidal use by thermal volatilization, use for oxygen absorption, and use for treating cancer in addition to common warming of a human body.
  • the heat generating body of the invention can be used for heat insulation of pets, machines, and the like.
  • Examples of a method for using the heat generating body include a method of use in which the heat generating body is applied to a site of the body which a person who requires the remedy has a pain, the temperature of the skin or the holding time is appropriately selected depending upon the person who requires the remedy, and a suffering is substantially relieved in comfort, thereby remedying the suffering due to an acute, recurrent or chronic muscular pain, a skeleton pain, or a related pain.
  • the process for producing the heat generating body is not limited, there are enumerated the following production processes.
  • the "air-permeable adjusting material" as referred to in the invention comprises a sectional exothermic part and a sectioned part and covers an exothermic part having a difference of altitude via an adhesive layer, etc., thereby adjusting the air permeability into the sectional exothermic part. That is, in the air permeability adjusting material, by covering the exothermic part by the air-permeable adjusting material while utilizing a difference of altitude between the sectional exothermic part and the sectioned part, a partitioned space is formed in at least a part of the periphery of the sectional exothermic part, thereby adjusting the air permeability between the outside and the sectional exothermic part and also imparting a heat insulating effect.
  • the air permeability of the air permeability adjusting material is not limited so far as it is able to adjust air retention or air permeability in at least a part of the periphery of the sectional exothermic part.
  • the air permeability of the air permeability adjusting material is lower than that on the air-permeable surface of the sectional exothermic part as a covering part for covering the heat generating composition molded body.
  • a region where the air permeability is higher than that in the covering part for covering the heat generating composition molded body may be provided in a local region of the air-permeable adjusting material, thereby keeping the air permeability of other region lower than that on the air-permeable surface of the sectional exothermic part.
  • the raw material which constitutes the air permeability adjusting material the raw material which is used in the packaging material to be used in the air-impermeable accommodating bag for sealing and accommodating the substrate, the covering material and the heat generating body of a chemical body warmer or heat generating body can be used.
  • An adhesive which is used in a chemical body warmer or heat generating body is preferable.
  • the heat generating body of the invention is able to give various shapes, thicknesses and temperature zones and therefore, can be used for various utilities such as use for a joint, facial esthetic use, use for eyes, slimming use, use for heating or warming a dripping solution, use for a wet compress pack, use for a medical body warmer, use for a neck, use for a waist, use for a mask, use for a glove, use for hemorrhage, use for relaxation of symptoms such as shoulder pain, muscular pain, and menstrual pain, use for a cushion, use for heating or warming a human body during the operation, use for a thermal sheet, use for thermally volatilizing an aroma, use for an abdomen, insecticidal use by thermal volatilization, and use for treating cancer in addition to common warming of a human body.
  • the heat generating body of the invention can be used for heating or warming machines, pets, etc.
  • the heat generating body of the invention is applied directly in a necessary site of the body or indirectly via a cloth, etc.
  • a method for using the heat generating body of the invention includes the following methods.
  • a stirring type batchwise oxidizing gas contact treatment device consisting of a mixer equipped with a rotary blade for stirring was used as an oxidizing gas contact treatment device, and air was used as an oxidizing gas.
  • a reaction mixture consisting of 100 parts by weight of a reduced iron powder (particle size: not more than 300 ⁇ m), 3.5 parts by weight of active carbon (particle size: not more than 300 ⁇ m), and 5 parts by weight of 11 % salt water and having a water mobility value of less than 0.01 was charged in the stirring type batchwise oxidizing gas contact treatment device.
  • the upper portion of the oxidizing gas contact treatment device was opened to air, the reaction mixture was subjected to self heat generation with stirring under circumstances at 25 °C, and at a point of time when the temperature reached 30 °C after 20 seconds, the reaction mixture was sealed in an air-impermeable accommodating bag and allowed to stand until the temperature reached room temperature, thereby obtaining a heat generating mixture of the invention.
  • 11 % salt water was added to and mixed with the heat generating mixture to obtain a heat generating composition having a water mobility value of 8.
  • Example 2 A reaction mixture the same as in Example 1 was not subjected to the oxidizing gas contact treatment, and 11 % by weight salt water was added to the reaction mixture, thereby obtaining a heat generating composition having a water mobility value of 8. Using the heat generating composition, a heat generating body was obtained in the same manner as in Example 1.
  • Example 1 The heat generating compositions of Example 1 and Comparative Example 1 were each subjected to an exothermic test of heat generating composition. As a result, as seen in the curves of Fig. 3, the heat generating composition of Example 1 reached about 35 °C after one minute and about 55 °C (an average value of five samples) after three minutes, respectively. In the heat generating composition of Comparative Example 1, the temperature was 23 °C after one minute and 28 °C (an average value of five samples) after three minutes, respectively. Comparative Example 1 was remarkably slow with respect to the temperature rise rate as compared with Example 1.
  • Example 1 From the test results of Example 1 and Comparative Example 1, it could be confirmed that the heat generating composition as prepared in Example 1 is excellent with respect to the exothermic rising properties.
  • a stirring type batchwise oxidizing gas contact treatment device consisting of a mixer equipped with a rotary blade for stirring was used as an oxidizing gas contact treatment device, and air was used as an oxidizing gas.
  • a reaction mixture consisting of 100 parts by weight of an iron powder (particle size: not more than 300 ⁇ m), 5.
  • the upper portion of the oxidizing gas contact treatment device was opened to air, the reaction mixture was subjected to self heat generation with stirring under circumstances at 20 °C, and at a point of time when the temperature reached 27 °C after 20 seconds, the reaction mixture was sealed in an air-impermeable accommodating bag and allowed to stand until the temperature reached room temperature, thereby obtaining a heat generating mixture of the invention.
  • 11 % salt water was added to and mixed with the heat generating mixture to obtain a heat generating composition having a water mobility value of 8.
  • This heat generating composition was subjected to the exothermic test of heat generating composition. As a result, the same results as in Example 1 were obtained.
  • the heat generating composition was tested for moldability. As a result, even after separating a trimming die from a heat generating composition molded body, the heat generating composition molded body was free from a loss of shape, and collapsed pieces of the heat generating composition molded body were not generated in the surroundings of the heat generating composition molded body.
  • an air-permeable substrate 3 having an adhesive layer 3B and a separator 3C provided on a polyethylene film 3A was used, and a rectangular heat generating composition molded body 2 having a plane of 2 mm in thickness, 115 mm in length and 80 mm in width was molded on the side of the polyethylene film 3A using a trimming die having a thickness of 2 mm and laminated on the substrate 3.
  • an air-permeable packaging material of a laminate of a nylon-made non-woven fabric 4A and a polyethylene-made porous film 4B was used as a covering material 4 and superimposed thereon such that the surface of the polyethylene film 3A and the surface of the porous film 4B were brought into contact with each other, and the periphery of the heat generating composition molded body was subjected to a heat seal 6A in a seal width of 8 mm, thereby preparing an irregular heat generating body 1 having a rectangular shape of 135 mm in length, 100 mm in width and 8 mm in seal width.
  • the air permeability of the covering material 4 was 370 g/m 2 /24 hr in terms of a moisture permeability by the Lyssy method.
  • the heat generating body was sealed and accommodated in an air-impermeable outer bag and allowed to stand at room temperature for 24 hours. An exothermic test by the body was carried out. As a result, it was felt warm after 3 minutes, and thereafter, the warmth was continued for 10 hours or more.
  • Example 2 A reaction mixture the same as in Example 2 was not subjected to the oxidizing gas contact treatment, and salt water of 11 % by weight was added to the reaction mixture, thereby obtaining a heat generating composition having a water mobility value of 8. As a result of the exothermic test of heat generating composition, the same results as in Comparative Example 1 were obtained. Furthermore, using the heat generating composition, a heat generating body was obtained in the same manner as in Example 2.
  • Example 2 With respect to Example 2 and Comparative Example 2, the exothermic test of heat generating body was carried out. As a result, as shown in Fig. 4, in the case of Example 2, the temperature was 40 °C after 10 minutes, 50 °C after 30 minutes and 58 °C after 3 hours, respectively. However, in the case of Comparative Example 2, the temperature was 35 °C after 10 minutes, 45 °C after 30 minutes and 55 °C after 3 hours, respectively.
  • the heat generating body using the heat generating composition of the invention was explicitly excellent with respect to the exothermic rising properties.
  • Fig. 5 is a cross-sectional view of the heat generating body 1 in which the substrate 3 of Example 2 is replaced by a substrate 3 having an SIS based adhesive layer 7 equipped with a separator 9.
  • Fig. 6 is a cross-sectional view of the heat generating body 1 in which the substrate of Example 2 is replaced by a hydrophilic adhesive layer 8 equipped with a separator 9.
  • a hydrophilic adhesive constituting the hydrophilic adhesive layer is a composition consisting of 4.5 % by weight of polyacrylic acid, 1.5 % by weight of poly(sodium acrylate), 4.0 parts by weight of sodium carboxymethyl cellulose, 15.0 % by weight of glycerin, 5.0 % by weight of propylene glycol, 10.0 % by weight of sorbitol, 0.1 % by weight of aluminum hydroxide, 0.05 % by weight of synthetic hydrotalcite, and 1. 0 % by weight of polyoxyethylene glycol, with the remainder being water.
  • Fig. 7 is an example in which a display 10 is provided in the heat generating body 1.
  • Example 1 To the heat generating mixture as obtained in Example 1, a mixture consisting of 100 parts by weight of an iron powder, 2.3 parts by weight of a water absorptive polymer (particle size: not more than 300 ⁇ m), 2. 3 parts by weight of a wood meal (particle size: not more than 300 ⁇ m), 0.7 parts by weight of sodium sulfite, and 0.2 parts by weight of calcium hydroxide (particle size: not more than 300 ⁇ m) as reduced into the reaction mixture was added. After mixing, 30 parts by weight of 11 % salt water was added and further mixed, thereby obtaining a heat generating composition. Its water mobility value was less than 0.01.
  • This heat generating composition was subjected to an exothermic test of heat generating composition to obtain 5 data in total.
  • the results of measuring the temperature revealed that the temperature was about 50 °C (an average value of five samples) after 3 minutes likewise Example 1.
  • the heat generating composition was tested for moldability. As a result, even after separating a trimming die from a heat generating composition molded body, the heat generating composition molded body was free from a loss of shape, and collapsed pieces of the heat generating composition molded body were not generated in the surroundings of the heat generating composition molded body.
  • packing material pieces of 135 mm in length x 100 mm in width were prepared by using an air-impermeable packaging material having an adhesive layer 8 and a separator 9 on a polyethylene film 3A as a substrate 3 and an air-permeable packaging material having a nylon-made non-woven fabric 4A and a porous polyethylene film 4B laminated in this order as a covering material 4, respectively, and a rectangular air-permeable flat accommodating bag, three sides of which were heat sealed in a seal width of 8 mm, was prepared.
  • the foregoing heat generating composition 25 g was charged in the flat accommodating bag, and the side which had not been heat sealed was heat sealed, thereby preparing a rectangular flat heat generating body 1 of 135 mm in length, 100 mm in width and 8 mm in seal width.
  • the air permeability of the covering material 4 was 370 g/m 2 /24 hr in terms of a moisture permeability by the Lyssy method.
  • the heat generating body was sealed and accommodated in an air-impermeable outer bag and allowed to stand at room temperature for 24 hours.
  • the heat generating body was taken out from the outer bag and subjected to an exothermic test.
  • the temperature after lapsing 30 minutes was 50 °C.
  • a temperature of 40 °C or higher was continued for 10 hours or more.
  • a heat generating composition was obtained in the same manner as in Example 3, except that the water mobility value was changed to 5. This heat generating composition was subjected to an exothermic test of heat generating composition. The measurement results revealed that the temperature after 3 minutes was about 49 °C (an average value of five samples).
  • a rectangular heat generating composition molded body of 125 mm in length x 90 mm in width was molded and laminated on the substrate by force-through molding. Next, the air-permeable covering material was covered thereon, and the surroundings of the heat generating composition molded body were heat sealed, thereby preparing a rectangular heat generating body of 135 mm in length x 100 mm in width in a seal width of 8 mm.
  • the heat generating body was sealed and accommodated in an air-impermeable outer bag and allowed to stand at room temperature for 24 hours. After 24 hours, the heat generating body was taken out from the outer bag and subjected to an exothermic test. The temperature after 30 minutes was 52 °C. A temperature of 40 °C or higher was continued for 10 hours or more.
  • Example 3 25 g of the heat generating composition as prepared in Example 3 was accommodated in a separator-protected adhesive layer-provided air-permeable accommodating bag, and the surroundings of the heat generating body were sealed in a seal width of 8 mm to prepare a rectangular flat heat generating body of 130 mm in length x 80 mm in width, which was then sealed in an air-impermeable outer bag.
  • the air permeability of an air-permeable part of the air-permeable accommodating bag was 400 g/m 2 /24 hr in terms of a moisture permeability by the Lyssy method.
  • the heat generating body was taken out from the outer bag and subjected to an exothermic test by the body. As a result, it was felt warm within 3 minutes, and thereafter, the warmth was continued for 10 hours or more.
  • a reaction mixture consisting of 100 parts by weight of an iron powder (particle size: not more than 300 ⁇ m), 6.5 parts by weight of active carbon (particle size: not more than 300 ⁇ m), 3 parts by weight of a water absorptive polymer (particle size: not more than 300 ⁇ m), 0.5 parts by weight of calcium hydroxide, 0.7 parts by weight of sodium sulfite, and 10 parts by weight of 11 % salt water and having a water mobility value of less than 0.01 was charged in a stirring type batchwise oxidizing gas contact treatment device under circumstances at 30 °C. The temperature of the reaction mixture at the time of charging was 20 °C.
  • Example 5 Next, the upper portion of the oxidizing gas contact treatment device vessel was opened to air, and at a point of time when the temperature reached 40 °C after one minute, 11 % salt water was added with stirring. Stirring and mixing were carried out for 10 seconds to form a heat generating composition having a water mobility value of 10.
  • a heat generating body was prepared in the same manner as in Example 5 and subjected to an exothermic test. As a result, the same results as in Example 5 were obtained.
  • the heat generating composition was tested for moldability. As a result, even after separating a trimming die from a heat generating composition molded body, the heat generating composition molded body was free from a loss of shape, and collapsed pieces of the heat generating composition molded body were not generated in the periphery of the heat generating composition molded body.
  • a stirring type batchwise oxidizing gas contact treatment device consisting of a mixer equipped with a rotary blade for stirring was used as an oxidizing gas contact treatment device, and air was used as an oxidizing gas.
  • a heat generating mixture consisting of 100 parts by weight of an iron powder (particle size: not more than 300 ⁇ m) having a content of wustite of less than 1 % by weight, 2.3 parts by weight of a wood meal (particle size: not more than 150 ⁇ m), 6.5 parts by weight of active carbon (particle size: not more than 300 ⁇ m), 2.
  • an air-permeable packaging material made of a laminate of a nylon-made non-woven fabric 4A and a polyethylene-made porous film 4B was used as a covering material 4 and superimposed thereon such that the surface of the polyethylene film and the surface of the porous film were brought into contact with each other.
  • the surroundings of each of the square heat generating composition molded bodies were then heat sealed in a seal width of 5 mm, thereby preparing a sectioned part 6.
  • the surroundings of the heat generating body were heat sealed in a seal width of 8 mm to prepare a heat generating body 1 having an outer dimension of 131 mm x 101 mm and containing 12 sectional exothermic parts 1B (see Fig. 8).
  • the heat generating composition molded body was free from a loss of shape, and collapsed pieces of the heat generating composition molded body were not generated in the periphery of the heat generating composition molded body. Also, sealing could be completely carried out without causing incorporation of collapsed pieces of the heat generating composition molded body into the seal part, and seal failure did not occur. The moldability was satisfactory.
  • the air permeability of the covering material 4 was 370 g/m 2 /24 hr in terms of a moisture permeability by the Lyssy method. The heat generating body 1 was sealed and accommodated in an air-impermeable outer bag and allowed to stand at room temperature for 24 hours.
  • the heat generating body was taken out from the outer bag and subjected to an exothermic test by the body. As a result, it was felt warm within 3 minutes, and an exothermic holding time of 34 °C or higher was 8.5 hours. Flexibility of the heat generating body was kept before, during and after the use. An adhesive strength of the adhesive layer beneath of the sectioned part 6 of this heat generating body is weaker than that of the adhesive layer beneath the sectional exothermic part 1B.
  • Fig. 9 is an example in which a seal part 6 is sealed in an irregular pattern, and perforations 7 which can be cut by hand are provided.
  • a heat generating composition having a water mobility value of 25 was obtained in the same manner as in Example 3, except for changing only the adjustment of the water content. Furthermore, the moldability of the heat generating composition was measured according to the foregoing measurement method for moldability. As a result, collapsed pieces of a heat generating composition molded body were not observed, and therefore, this heat generating composition was a moldable heat generating composition.
  • an air-impermeable packaging material having a 40 ⁇ m-thick air-impermeable polyethylene film stuck on one surface of a liner paper (thickness: 300 ⁇ m) was used as a substrate, and the foregoing heat generating composition was molded and laminated on the liner paper of the substrate by force-through molding using a trimming die having a rectangular cavity of 2 mm in thickness, 120 mm in length and 84 mm in width, thereby obtaining a heat generating composition molded body. Collapsed pieces of a heat generating composition molded body were not observed in the periphery of the heat generating composition molded body, and the moldability was satisfactory.
  • a covering material in which a network-like adhesive layer provided with a styrene-isobutene-styrene block copolymer based sticky polymer in a network form by the melt blow method was provided in the side of a polyethylene-made porous film was superimposed thereon such that the network-like adhesive layer surface of the covering material and the heat generating composition molded body were brought into contact with each other.
  • the periphery of the heat generating composition molded body was sealed by compression seal, and the circumference was cut, thereby producing a rectangular flat heat generating body of 136 mm in length, 100 mm in width and 8 mm in seal width.
  • the heat generating body was sealed in an outer bag which is an air-impermeable accommodating bag and then allowed to stand for 24 hours.
  • a laminate of a craft paper having a thickness of 30 ⁇ m, a polyethylene-made porous film having a thickness of 50 ⁇ m, and a nylon non-woven fabric having a thickness of 150 ⁇ m in this order was used as the covering material.
  • the network-like adhesive layer was provided on the craft paper.
  • the air permeability of the covering material was 650 g/m 2 /24 hr in terms of a moisture permeability by the Lyssy method.
  • the heat generating body was taken out from the outer bag and subjected to an exothermic test by the body. As a result, it was felt warm within 3 minutes, and a period of time when it was felt warm was so long as 8 hours.
  • Fig. 10 shows an embodiment of the force-through molding method using a leveling plate 15. That is, a substrate 3 in a roll film form having a width of 130 mm is adapted to a molding mold 12 having a thickness of 1 mm and having a desired shape punched out in the center thereof and horizontally sent at a prescribed speed between a die 11 as disposed in the upper surface and a magnet 13 as disposed in the lower surface.
  • the heat generating composition 2 of Example 5 is sent into a mold hole 12a from the upper surface of the mold 12 through a hole 11a of the die 11.
  • the heat generating composition 2B is leveled in the same level as in the mold 12 by a leveling plate 15 as placed forward in the advancing direction and accommodated in the mold hole 12a, whereby a shape having a thickness of 1.5 mm is molded on the substrate 3. Thereafter, the mold 12 is removed to obtain a heat generating composition molded body as laminated on the substrate 3.
  • a styrene-isoprene-styrene block copolymer (SIS) based sticky polymer is then provided in a network-like form on the surface of the heat generating composition molded body by the melt blow method, a covering material is covered thereon, and the periphery of the heat generating composition molded body is sealed by heat seal, followed by cutting into a desired shape. There is thus obtained a heat generating body having a desired shape.
  • the cut heat generating body is subsequently sent into a packaging step and sealed in an air-tight outer bag.
  • the same molding is possible even by changing the leveling plate by a pushing leveling plate.
  • Fig. 11 shows a leveling plate 15
  • Fig. 12 shows a pushing leveling plate 15A. Incidentally, so far as a pushing leveling function is kept, the tip of the pushing leveling plate may be rounded by trimming, namely, it may be deformed in any form by means of rounding, etc.

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EP05765809A 2004-07-14 2005-07-14 Procédé de fabrication d'un mélange exothermique, mélange exothermique, composition exothermique et article exothermique Withdrawn EP1782780A4 (fr)

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JPWO2006006645A1 (ja) 2008-05-01
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WO2006006645A1 (fr) 2006-01-19
US20080283036A1 (en) 2008-11-20

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